JP5705179B2 - Nitride semiconductor wafer, nitride semiconductor device, and method for growing nitride semiconductor crystal - Google Patents

Description

  Embodiments described herein relate generally to a nitride semiconductor wafer, a nitride semiconductor device, and a method for growing a nitride semiconductor crystal.

  Nitride semiconductors are used in various fields such as optical devices typified by light-emitting / light-receiving elements and high-speed electronic devices typified by high-frequency elements.

  When a nitride semiconductor crystal is formed on a silicon substrate excellent in mass productivity, defects such as cracks due to a difference in lattice constant or thermal expansion coefficient are likely to occur. In order to obtain high performance, a high-quality crystal with few dislocations is desired.

US Pat. No. 7,825,432B2

  Embodiments of the present invention provide a nitride semiconductor wafer, a nitride semiconductor device, and a method for growing a nitride semiconductor crystal, which are formed on a silicon substrate and have few dislocations and cracks.

According to the embodiment of the present invention, a nitride semiconductor wafer having a silicon substrate, a lower strain relaxation layer, an intermediate layer, an upper strain relaxation layer, and a functional layer is provided. The lower strain relaxation layer is provided on the main surface of the silicon substrate and includes a nitride semiconductor layer. The intermediate layer is provided on the lower strain relaxation layer and includes a nitride semiconductor. The upper strain relaxation layer is provided on the intermediate layer and includes a nitride semiconductor layer. The functional layer is provided on the upper strain relaxation layer and includes a nitride semiconductor. The intermediate layer includes a first lower layer of a thickness of less than 500nm or 100 nm, a first doped layer of a thickness of less than 150nm or more 20 nm, a first upper layer of a thickness of less than 500nm or 100 nm, the . The first lower layer includes a nitride semiconductor provided on the lower strain relaxation layer and having a lattice constant larger than the lattice constant of the nitride semiconductor of the lower strain relaxation layer. The first doped layer is provided on the first lower layer. The first doped layer has a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the first lower layer and has a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ . 1 Nitriding containing impurities including at least one of silicon (Si), magnesium (Mg), manganese (Mn), iron (Fe), oxygen (O), and carbon (C) at a higher concentration than the lower layer Includes physical semiconductors. The first upper layer is provided on the first doped layer. The first upper layer is a nitride semiconductor having a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the first doped layer and larger than the lattice constant of the nitride semiconductor of the first lower layer. Including.
According to another embodiment of the present invention, a nitride semiconductor device includes an intermediate layer that is formed on a main surface of a silicon substrate and includes a nitride semiconductor, and an upper layer that is provided on the intermediate layer and includes a nitride semiconductor layer. A strain relaxation layer; and a functional layer provided on the upper strain relaxation layer and including a nitride semiconductor. The intermediate layer is formed on the main surface and includes a first lower layer having a thickness of 100 nm or more and 500 nm or less including a nitride semiconductor, and the intermediate layer is provided on the first lower layer and is formed on the first lower layer. Silicon (Si) having a lattice constant greater than or equal to the lattice constant of the nitride semiconductor, having a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ and higher than the first lower layer. First, having a thickness of 20 nm or more and 150 nm or less, including a nitride semiconductor containing an impurity including at least one of magnesium, Mg (Mg), manganese (Mn), iron (Fe), oxygen (O), and carbon (C) A doped layer and a lattice that is provided on the first doped layer and is greater than or equal to the lattice constant of the nitride semiconductor of the first doped layer and greater than the lattice constant of the nitride semiconductor of the first lower layer Nitride semiconductors with constants A first upper layer having a thickness of 100 nm to 500 nm including the body.
According to another embodiment of the present invention, a lower strain relaxation layer including a nitride semiconductor is formed on a main surface of a silicon substrate, and the lower strain relaxation layer is nitrided on the lower strain relaxation layer. Forming a first lower layer having a thickness of not less than 100 nm and not more than 500 nm including a nitride semiconductor having a lattice constant larger than that of the physical semiconductor, and forming the first lower layer on the first lower layer. Silicon (Si) having a lattice constant greater than or equal to the lattice constant of the nitride semiconductor, having a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ and higher than the first lower layer, First dope with a thickness of 20 nm or more and 150 nm or less including a nitride semiconductor containing an impurity including at least one of magnesium (Mg), manganese (Mn), iron (Fe), oxygen (O), and carbon (C) Forming a layer on the first doped layer Including a nitride semiconductor having a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the first doped layer and greater than the lattice constant of the nitride semiconductor of the first lower layer. Forming a first upper layer having a thickness, forming an intermediate layer, forming an upper strain relaxation layer including a nitride semiconductor layer on the intermediate layer, and forming a nitride semiconductor on the upper strain relaxation layer; A method of growing a nitride semiconductor crystal that forms a functional layer is provided.

1 is a schematic cross-sectional view showing a nitride semiconductor wafer according to a first embodiment. 1 is a schematic cross-sectional view showing a part of a nitride semiconductor wafer according to a first embodiment. FIG. 3A to FIG. 3D are atomic force microscope photographic images showing a part of the nitride semiconductor wafer. FIG. 4A and FIG. 4B are graphs showing the characteristics of the nitride semiconductor wafer. FIG. 5A and FIG. 5B are graphs showing the characteristics of the nitride semiconductor wafer. FIGS. 6A and 6B are schematic cross-sectional views showing another nitride semiconductor wafer according to the first embodiment. FIG. 7A and FIG. 7B are schematic cross-sectional views showing another nitride semiconductor wafer according to the first embodiment. FIGS. 8A and 8B are graphs showing the nitride semiconductor crystal according to the first embodiment. It is a flowchart figure which shows the growth method of the nitride semiconductor crystal which concerns on 2nd Embodiment. It is a flowchart figure which shows the growth method of the nitride semiconductor crystal which concerns on 2nd Embodiment. FIG. 6 is a schematic cross-sectional view showing a nitride semiconductor device according to a third embodiment. It is a typical sectional view showing another nitride semiconductor device concerning a 3rd embodiment.

Each embodiment will be described below with reference to the drawings.
The drawings are schematic or conceptual, and the relationship between the thickness and width of each part, the size ratio between the parts, and the like are not necessarily the same as actual ones. Further, even when the same part is represented, the dimensions and ratios may be represented differently depending on the drawings.
Note that, in the present specification and each drawing, the same elements as those described above with reference to the previous drawings are denoted by the same reference numerals, and detailed description thereof is omitted as appropriate.

(First embodiment)
The first embodiment relates to a nitride semiconductor wafer. The nitride semiconductor wafer is provided with, for example, at least a part of the semiconductor device or a part that becomes at least a part of the semiconductor device. The semiconductor device includes, for example, a semiconductor light emitting element, a semiconductor light receiving element, and an electronic device. The semiconductor light emitting element includes, for example, a light emitting diode (LED) and a laser diode (LD). The semiconductor light receiving element includes a photodiode (PD) and the like. The electronic device includes, for example, a high electron mobility transistor (HEMT), a heterojunction bipolar transistor (HBT), a field transistor (FET), a Schottky barrier diode (SBD), and the like.

FIG. 1 is a schematic cross-sectional view illustrating the configuration of a nitride semiconductor wafer according to the first embodiment.
As shown in FIG. 1, the nitride semiconductor wafer 110 according to this embodiment includes a silicon substrate 50, a lower strain relaxation layer 51, an intermediate layer 55, an upper strain relaxation layer 52, a functional layer 40, including.

  The silicon substrate 50 has a main surface 50a. The silicon substrate 50 is, for example, a Si (111) substrate. However, the embodiment is not limited to this, and the plane orientation of the silicon substrate 50 is arbitrary.

  The lower strain relaxation layer 51 is provided on the main surface 50 a of the silicon substrate 50. Lower strain relaxation layer 51 includes a nitride semiconductor. For the lower strain relaxation layer 51, for example, AlN is used. More specifically, a low-temperature grown AlN layer is used for the lower strain relaxation layer 51. The lower strain relaxation layer 51 can have a function as a nucleation layer provided on the main surface 50 a of the silicon substrate 50. The thickness of the lower strain relaxation layer 51 is, for example, 10 nanometers (nm) or more and 200 nm or less.

  The intermediate layer 55 is provided on the lower strain relaxation layer 51. The intermediate layer 55 includes a nitride semiconductor.

The upper strain relaxation layer 52 is provided on the intermediate layer 55. Upper strain relaxation layer 52 includes a nitride semiconductor layer. For the upper strain relaxation layer 52, for example, Al _z0 Ga _1-z0 N (0 <z0 ≦ 1) is used. For the upper strain relaxation layer 52, for example, AlN or AlGaN is used.

  The functional layer 40 is provided on the upper strain relaxation layer 51. The functional layer 40 includes a nitride semiconductor. The functional layer 40 includes, for example, a layer having a light emitting function of a semiconductor light emitting element. The functional layer 40 includes, for example, a layer having a light receiving function of a semiconductor light receiving element. The functional layer 40 includes, for example, a layer having at least one function of rectification, switching, and amplification of an electronic device. An example of the configuration of the functional layer 40 will be described later.

  The intermediate layer 55 includes a first lower layer LA1, a first doped layer LB1, and a first upper layer LC1. The first lower layer LA1 is provided on the lower strain relaxation layer 51. The first lower layer LA1 includes a nitride semiconductor. The nitride semiconductor included in the first lower layer LA1 has a lattice constant larger than that of the nitride semiconductor of the lower strain relaxation layer 51.

  In the present specification, the “lattice constant” is a lattice constant in the a-axis direction.

The first doped layer LB1 is provided on the first lower layer LA1. The first doped layer LB1 includes a nitride semiconductor. The nitride semiconductor included in the first doped layer LB1 has a lattice constant greater than or equal to the lattice constant of the first lower layer LA1. The first doped layer LB1 contains impurities at a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ .

  The first upper layer LC1 is provided on the first doped layer LB1. The first upper layer LC1 includes a nitride semiconductor. The nitride semiconductor included in the first upper layer LC1 has a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the first doped layer LB1 and larger than the lattice constant of the nitride semiconductor of the first lower layer LA1.

  The intermediate layer 55 includes a first stacked film SL1. The first stacked film SL1 includes the first lower layer LA1, the first doped layer LB1, and the first upper layer LC1. However, as will be described later, the intermediate layer 55 may have a configuration of a plurality of laminated films.

  Here, a direction from the first lower layer LA1 toward the first upper layer LC1 is defined as a stacking direction (Z-axis direction). The stacking direction is parallel to the direction from the silicon substrate 50 toward the functional layer 40.

  In the first stacked film SL1, the lattice constant increases in the stacking direction (in the direction from the first lower layer LA1 to the first upper layer LC1). When the lattice constant of the first lower layer LA1 is a1, the lattice constant of the first doped layer LB1 is b1, and the lattice constant of the first upper layer LC1 is c1, a1 <c1. Then, a1 <b1 <c1 or a1 ≦ b1 <c1 or a1 <b1 ≦ c1.

For example, the first lower layer LA1 includes Al _xa1 In _ya1 Ga _1-xa1-ya1 N (0 ≦ xa1 <1, 0 ≦ ya1 <1, xa1 + ya ≦ 1). The first doped layer LB1 includes Al _xb1 In _yb1 Ga _1-xb1-yb1 N (0 ≦ xb1 <1, 0 ≦ yb1 <1, xb1 + yb1 ≦ 1). The first upper layer LC1 includes Al _xc1 In _yc1 Ga _1-xc1-yc1 N (0 ≦ xc1 <1, 0 ≦ yc1 <1, xc1 + yc1 ≦ 1).

For example, the first lower layer LA1 includes Al _xa1 Ga _1-xa N (0 <xa1 ≦ 1). The first doped layer LB1 includes Al _xb1 Ga _1-xb1 N (0 <xb1 <xa1). The first upper layer LC1 includes Al _xc1 Ga _1-xc1 N (0 ≦ xc1 <xb1).

  For example, the composition ratio of the first doped layer LB1 is different from the composition of the first lower layer LA1, and is different from the composition ratio of the first upper layer LC1. The lattice constant of the first doped layer LB1 is larger than the lattice constant of the first lower layer LA1 and smaller than the lattice constant of the first upper layer LC1.

For example, an Al _0.5 Ga _0.5 N layer is used for the first lower layer LA1. For example, an Al _0.2 Ga _0.8 N layer is used for the first doped layer LB1. For the first upper layer LC1, for example, a GaN layer is used.

  The thickness of the first lower layer LA1 is, for example, not less than 100 nm and not more than 500 nm. The thickness of the first doped layer LB1 is, for example, not less than 20 nm and not more than 150 nm. The thickness of the first upper layer LC1 is not less than 100 nm and not more than 500 nm.

  The impurities contained in the first doped layer LB1 include, for example, at least one of silicon (Si) and magnesium (Mg). Further, the impurities can include, for example, at least one of Si, Mg, manganese (Mn), iron (Fe), oxygen (O), and carbon (C).

  As described above, in the nitride semiconductor wafer 110 according to the present embodiment, the intermediate layer 55 includes the stacked film (for example, the first stacked film SL1), and the first stacked film SL1 is along the stacking direction. Lattice constant increases. Thereby, compressive strain is applied in the first stacked film SL1. Thereby, a crack is suppressed. In the first stacked film SL1, the compressive strain increases in the stacking direction.

  Further, in the first stacked film SL1, the first doped layer LB1 doped with impurities is disposed between the first lower layer LA1 having a small lattice constant and the first upper layer LC1 having a large lattice constant. . This reduces dislocations.

  According to the embodiment, a nitride semiconductor wafer formed on a silicon substrate with few dislocations and cracks can be provided. That is, the dislocation density and crack density are simultaneously reduced.

FIG. 2 is a schematic cross-sectional view illustrating the configuration of a part of the nitride semiconductor wafer according to the first embodiment.
FIG. 2 illustrates the configuration of the functional layer 40 when the nitride semiconductor wafer 110 is applied to a semiconductor light emitting device.

  As illustrated in FIG. 2, in this example, the functional layer 40 includes the first semiconductor layer 10, the second semiconductor layer 20, and the light emitting unit 30. The first semiconductor layer 10 is provided on the upper strain relaxation layer 52. The first semiconductor layer 10 includes a nitride semiconductor and has a first conductivity type. The second semiconductor layer 20 is provided on the first semiconductor layer 10. The second semiconductor layer 20 includes a nitride semiconductor and has a second conductivity type different from the first conductivity type. For example, the first conductivity type is n-type and the second conductivity type is p-type. The first conductivity type may be p-type and the first conductivity type may be n-type.

  The light emitting unit 30 is provided between the first semiconductor layer 10 and the second semiconductor layer 20. The light emitting unit 30 includes a plurality of barrier layers 31 and a well layer 32 provided between the plurality of barrier layers 31. The number of well layers 32 may be one or plural. That is, the light emitting unit 30 can have an SQW (Single-Quantum Well) structure or an MQW (Multi-Quantum Well) structure.

  The band gap energy of the barrier layer 31 is larger than the band gap energy of the well layer 32. For the well layer 32, for example, InGaN is used. GaN is used for the barrier layer 31. When InGaN is used for the barrier layer 31, the In composition ratio in the barrier layer 31 is smaller than the In composition ratio in the well layer 32. The peak wavelength of light emitted from the light emitting unit 30 is, for example, not less than 200 nm and not more than 1300 nm.

  In the specification of the present application, “the state in which the second layer is provided on the first layer” refers to the state of the first layer in addition to the state in which the second layer is disposed in contact with the first layer on the first layer. It also includes a state in which the third layer is inserted above and the second layer is disposed on the third layer.

  The nitride semiconductor wafer 110 is manufactured as follows, for example. A lower strain relaxation layer 51 is formed on the main surface 50a of the silicon substrate 50, a first lower layer LA1 is formed thereon, a first doped layer LB1 is formed thereon, and a first doped layer LB1 is formed thereon. Upper layer LC1 is formed. Further, the upper strain relaxation layer 52 is formed thereon, and the functional layer 40 is formed thereon.

  Specifically, the following crystal layer is formed on the main surface 50a of the silicon substrate 50 by using, for example, the MOVPE method. First, a low temperature growth AlN layer to be the lower strain relaxation layer 51 is formed. The formation temperature of the lower strain relaxation layer 51 is, for example, 900 ° C. or less. The formation temperature of the lower strain relaxation layer 51 is about 700 ° C., for example. The thickness of the lower strain relaxation layer 51 is, for example, 30 nm.

Furthermore, an Al _0.5 Ga _0.5 N layer to be the first lower layer LA1 is formed thereon. The formation temperature of the first lower layer LA1 is, for example, 1100 ° C. The thickness of the first lower layer LA1 is, for example, about 300 nm.

Furthermore, an Al _0.2 Ga _0.2 N layer to be the first doped layer LB1 is formed thereon. The formation temperature of the first doped layer LB1 is, for example, about 1100 ° C. For example, the first doped layer LB1 is doped with Mg at a high concentration. The concentration of Mg in the first doped layer LB1 is 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ .

  Furthermore, a GaN layer to be the first upper layer LC1 is formed thereon. The formation temperature of the first upper layer LC1 is 1120 ° C., for example. The thickness of the first upper layer LC1 is, for example, 600 nm.

  Further, a low temperature growth AlN layer to be the upper strain relaxation layer 52 is formed thereon. As the upper strain relaxation layer 52, a low-temperature grown AlGaN layer may be used. The formation temperature of the upper strain relaxation layer 52 is, for example, 900 ° C. or less. The formation temperature of the upper strain relaxation layer 52 is about 700 ° C., for example. The thickness of the upper strain relaxation layer 52 is, for example, 15 nm.

Further, an n-type GaN layer to be the first semiconductor layer 10 is formed on the upper strain relaxation layer 52. The formation temperature of the first semiconductor layer 10 is 1100 ° C., for example. For example, Si is doped into the first semiconductor layer 10. The thickness of the first semiconductor layer 10 is, for example, 2 micrometers (μm). Further, an In _0.15 Ga _0.85 N layer to be the well layer 32 and a GaN layer to be the barrier layer 31 are stacked thereon at, for example, 750 ° C. to form the light emitting unit 30. Further on this, a p-type GaN layer to be the second semiconductor layer 20 is formed. The second semiconductor layer 20 is doped with Mg. The formation temperature of the second semiconductor layer 20 is, for example, 950 ° C.

  Thereby, the nitride semiconductor wafer 110 according to the present embodiment is formed. Further, after forming the p-side electrode and the n-side electrode, the semiconductor light-emitting element is formed by dividing into individual elements.

  In the nitride semiconductor wafer according to the present embodiment, in the laminated film (for example, the first laminated film SL1) of the intermediate layer 55, the lattice constant increases along the lamination direction, so that compressive strain is applied in the first laminated film SL1. Is done. Thereby, a crack is suppressed. Further, the warpage of the wafer is reduced. Furthermore, dislocations are reduced by the three-dimensional crystal growth due to the arrangement of the first doped layer LB1 in the first stacked film SL1. For example, when the first doped layer LB1 is provided in the first stacked film SL1, the surface of the first doped layer LB1 and the first upper layer LC1 formed on the first doped layer LB1 becomes uneven, and when the surface is planarized again. Dislocations are reduced.

  According to the embodiment, a nitride semiconductor wafer formed on a silicon substrate with few dislocations and cracks can be provided. That is, the dislocation density and crack density are simultaneously reduced.

  As a substrate for forming a nitride semiconductor device, a sapphire substrate is often used. In addition, the use of a silicon carbide substrate or a silicon substrate has been studied. A silicon substrate can be easily cut or cut as compared to a sapphire substrate and a silicon carbide substrate. In addition, the cost of the silicon substrate can be easily reduced. Further, the silicon substrate can have conductivity, and the silicon substrate can be used as a current path. However, since the difference in lattice constant between the silicon substrate and the nitride semiconductor is large, when the nitride semiconductor is formed on the silicon substrate, the transition density tends to be higher than when it is formed on the sapphire substrate. Moreover, since the difference in thermal expansion coefficient between the silicon substrate and the nitride semiconductor is large, cracks are likely to occur.

  On the other hand, there is a configuration (first reference example) in which first layers containing impurities and second layers not containing impurities are alternately stacked on a silicon substrate. In this configuration, the composition of the second layer is the same as the composition of the first layer. In this case, since the compositions of the first layer and the second layer are the same, the lattice constants of these layers are also the same. For this reason, compressive stress is not generated by these layers. In such a first reference example, a crack occurs in the nitride semiconductor layer when the temperature is lowered from the growth temperature to room temperature due to a large difference in thermal expansion coefficient between the silicon substrate and the nitride semiconductor layer. easy.

  On the other hand, a nucleation layer, an Al composition gradient layer, a first nitride semiconductor layer, a strain relaxation intermediate layer, and a second nitride semiconductor layer are stacked in this order on a silicon substrate, and the first nitride semiconductor layer and the strain relaxation are laminated. There is a configuration (second reference example) in which an SiN layer or an MgN layer is disposed between the intermediate layer and the intermediate layer. With this configuration, an attempt is made to reduce dislocations in the second nitride semiconductor layer by the mask effect.

  However, according to the experiments by the inventors of the present application, when the first doped layer LB1 of the intermediate layer 55 is doped with Si or Mg at a certain high concentration, SiN or MgN is easily formed. When the SiN layer or the MgN layer is formed, it is difficult to sufficiently reduce dislocations.

In the first doped layer LB1, the position of the group III element of the group III nitride semiconductor crystal is replaced by the impurity and enters the lattice position, so that the crystal state is maintained and no discontinuous portion is generated in the crystal. If discontinuous parts occur in the crystal, new dislocations / defects may be generated therefrom. When the impurity concentration such as Si and Mg is high, the impurity does not enter the lattice position but appears at the interstitial position, the impurity forms a direct bond with the nitrogen atom, and foreign matter such as Si-N or Mg-N enters the crystal. May occur. By making the impurity concentration less than 1 × 10 ²¹ cm ⁻³ , it is possible to suppress the generation of foreign matters in the crystal.

In the present embodiment, the impurity concentration in the first doped layer LB1 is not less than 1 × 10 ¹⁸ cm ^{−3 and} less than 1 × 10 ²¹ cm ⁻³ . In the first doped layer LB1, the doped impurity element (for example, at least one of Si, Mg, Mn, Fe, O, and C) is disposed at the lattice position of the nitride semiconductor of the first doped layer LB1. The impurity element is introduced to such an extent that the element entering the lattice position is replaced. For example, a compound such as SiN or MgN is not formed due to the introduced impurities.

  Due to the doped impurities, crystals grow three-dimensionally in the first doped layer LB1 (and the first upper layer LC1 formed thereon), and the surface irregularities become large. As a result, the density of dislocations (edge dislocation: edge dislocation and screw dislocation) decreases.

FIG. 3A to FIG. 3D are atomic force microscopic photographic images illustrating the configuration of part of the nitride semiconductor wafer.
These drawings show examples of experimental results conducted by the inventors. 3A to 3D correspond to the first to fourth samples S01 to S04, respectively. The first sample S01 is a sample in which the first doped layer LB1 is not formed. The second sample S02 corresponds to a sample into which Si is introduced at 8.9 × 10 ⁻³ μmol / min when forming the first doped layer LB1. The concentration of Si in the second sample S02 corresponds to 4 × 10 ¹⁹ cm ⁻³ . The third sample S03 corresponds to a sample into which Si is introduced at 8.9 × 10 ⁻² μmol / min when forming the first doped layer LB1. The concentration of Si in the third sample S03 corresponds to 4 × 10 ²⁰ cm ⁻³ . The fourth sample S04 corresponds to a sample into which Mg is introduced at 5.8 × 10 ⁻¹ μmol / min when the first doped layer LB1 is formed. The concentration of Mg in the fourth sample S04 corresponds to 5 × 10 ¹⁸ cm ⁻³ . FIGS. 3A to 3D show layers obtained by observing the upper surface of the first upper layer LC1 (GaN layer in this example) with an atomic force microscope (AFM) in the first to fourth samples S01 to S04. Illustrated.

  As shown in FIG. 3A, the surface of the first sample S01 without the first doped layer LB1 is flat. The surface roughness Ra (arithmetic average roughness) is 0.34 nm.

  As shown in FIG. 3B, in the second sample S02, unevenness is formed on the surface of the first upper layer LC1 (GaN layer in this example). That is, the GaN layer is formed in an island shape. The surface roughness Ra in the second sample S02 is 3.77 nm.

  As shown in FIG. 3C, in the third sample S02 having a high Si concentration, the formation of islands of the GaN layer is further promoted. The surface roughness Ra of the third sample S03 is 38.7 nm. Thus, by increasing the impurity concentration in the first doped layer LB1, the island-like growth of the GaN layer is promoted, and the height of the surface irregularities of the GaN layer is significantly increased.

  As shown in FIG. 3D, in the fourth sample S04 doped with Mg, the GaN layer is formed in an island shape, and irregularities are formed on the surface of the GaN layer. The surface roughness Ra of the fourth sample S04 is 13.2 nm.

  As described above, by providing the first doped layer LB1 doped with impurities, irregularities are formed on the surface of the first upper layer LC1 formed thereon, and a three-dimensional island-like crystal is obtained. By forming irregularities on the surface, the formed dislocation proceeds along the lateral direction (direction having a component perpendicular to the Z-axis direction) and is connected to, for example, another dislocation. As a result, the density of dislocations extending in the Z-axis direction decreases.

The influence on the unevenness of the first upper layer LC1 on the first doped layer LB1 varies depending on the type of impurities doped in the first doped layer LB1. The size of the unevenness is also affected by the growth conditions. However, the impurity concentration that brings about the effect of reducing the dislocation density is generally in the range of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ .

FIG. 4A and FIG. 4B are graphs illustrating characteristics of the nitride semiconductor wafer.
These drawings show the relationship between the concentration of Si and the dislocation density when Si is used as an impurity doped in the first doped layer LB1. 4A and 4B also show the characteristics of the semiconductor light emitting device 190 of the reference example in which the first doped layer LB1 is not provided. The vertical axis in FIG. 4A is the edge dislocation density EDD. The vertical axis of FIG. 4B is the screw dislocation density SDD. In these figures, the horizontal axis represents the impurity concentration C (Si) in the first doped layer LB1.

As shown in FIG. 4A, in the semiconductor light emitting device 190 without the first doped layer LB1, the edge dislocation density EDD is as high as about 1.3 × 10 ¹⁰ cm ⁻² . On the other hand, when the first doped layer LB1 doped with Si is provided (in this example, the impurity concentration C (Si) is 4 × 10 ¹⁹ / cm ³ to 4 × 10 ²⁰ / cm ³ ), the edge dislocations are formed. The density EDD is significantly reduced from about 1.3 × 10 ⁹ cm ⁻² to about 4.1 × 10 ⁹ cm ⁻² .

On the other hand, as shown in FIG. 4B, in the semiconductor light emitting device 190 in which the first doped layer LB1 is not provided, the screw dislocation density SDD is as large as about 3.3 × 10 ⁸ cm ⁻² . On the other hand, when the first doped layer LB1 doped with Si is provided, the screw dislocation density SDD is remarkably reduced from about 1.5 × 10 ⁸ cm ⁻² to about 2.1 × 10 ⁸ cm ^−2. doing.

FIG. 5A and FIG. 5B are graphs illustrating characteristics of the nitride semiconductor wafer.
These drawings show the relationship between the Mg concentration and the dislocation density when Mg is used as the impurity doped in the first doped layer LB1. The vertical axis | shaft of Fig.5 (a) is edge dislocation density EDD. The vertical axis in FIG. 5B is the screw dislocation density SDD. In these figures, the horizontal axis represents the impurity concentration C (Mg) in the first doped layer LB1.

As shown in FIG. 5A, the edge dislocation density EDD of the semiconductor light emitting device 190 is about 1.3 × 10 ¹⁰ cm ⁻² , whereas the first doped layer LB1 doped with Mg is provided. In this case (in this example, the impurity concentration C (Mg) is 1.4 × 10 ¹⁸ / cm ^{3 to} 2.8 × 10 ¹⁸ / cm ³ ), the edge dislocation density EDD is about 4.2 × 10 ⁹ cm. ^-2 to about 6.8 × 10 ⁹ cm ^-2 .

As shown in FIG. 5B, the semiconductor light emitting device 190 has a screw dislocation density SDD of about 3.3 × 10 ⁸ cm ⁻² , whereas the Mg-doped first doped layer LB1 is provided. In the case, the screw dislocation density SDD is significantly reduced to about 2.1 × 10 ⁸ cm ⁻² .

In the embodiment, in forming the first doped layer LB1, in order to introduce elements such as Si and Mg into the first doped layer LB1 as impurities, together with a gas used as a material for the nitride semiconductor, Si, Mg, etc. Impurity source gas is introduced into the reaction vessel. For example, a source gas serving as an impurity is introduced together with a group III source gas and a group V source gas to be an AlGaN layer (for example, an Al _xb1 In _yb1 Ga _1-xb1-yb1 N layer) to be the first doped layer LB1. Thereby, the impurity element is taken into the nitride semiconductor as an impurity. On the other hand, for example, when a gas containing nitrogen and a source gas containing an impurity element are introduced without introducing a gas containing Ga, the impurity element forms a compound such as SiN or MgN.

FIGS. 6A and 6B are schematic cross-sectional views illustrating the configuration of another nitride semiconductor wafer according to the first embodiment.
As shown in FIG. 6A, in another nitride semiconductor wafer 111 according to the present embodiment, the intermediate layer 55 includes a second lower layer LA2, a second doped layer LB2, and a second upper layer. And LC2. The second lower layer LA2 is provided on the first upper layer LC1. The second lower layer includes a nitride semiconductor having a lattice constant smaller than that of the first upper layer LC1. The second doped layer LB2 is provided on the second lower layer LA2. The second doped layer LB2 includes a nitride semiconductor. The nitride semiconductor included in the second doped layer LB2 has a lattice constant greater than or equal to the lattice constant of the second lower layer LA2. The nitride semiconductor included in the second doped layer LB2 contains impurities at a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ . The second upper layer LC2 is provided on the second doped layer LB2. The second upper layer LC2 includes a nitride semiconductor. The nitride semiconductor layer included in the second upper layer LC2 has a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the second doped layer LB2 and greater than the lattice constant of the nitride semiconductor of the second lower layer LA2.

  As described above, the intermediate layer 55 further includes the second stacked film SL <b> 2 provided between the first stacked film SL <b> 1 and the upper strain relaxation layer 52. The second stacked film SL2 includes a second lower layer LA2, a second doped layer LB2, and a second upper layer LC2.

In this example, the intermediate layer 55 further includes a second strain relaxation layer LD2. That is, the second stacked film SL2 further includes the second strain relaxation layer LD2. The second strain relaxation layer LD2 is provided between the first upper layer LC1 and the second lower layer LA2. The second strain relaxation layer LD2 includes a nitride semiconductor having a lattice constant smaller than that of the nitride semiconductor of the second lower layer LA2. _{Alz2Ga1 -z2N} (0 <z2 ≦ 1) is used for the second strain relaxation layer LD2. For example, an AlN layer is used for the second strain relaxation layer LD2. For example, when the second strain relaxation layer LD2 includes AlGaN, the Al composition ratio is higher than the Al composition ratio in the second lower layer LA2. The second strain relaxation layer LD2 may be regarded as the portion of the second lower layer LA2 closest to the silicon substrate 50.

For example, second lower layer LA2 _{includes Al xa2 In ya2 Ga 1-xa2} -ya2 N (0 ≦ xa2 <1,0 ≦ ya2 <1, xa2 + ya2 ≦ 1). The second doped layer LB2 includes Al _xb2 In _yb2 Ga _1-xb2-yb2 N (0 ≦ xb2 <1, 0 ≦ yb2 <1, xb2 + yb2 ≦ 1). Second upper layer LC2 _{includes Al xc2 In yc2 Ga 1-xc2} -yc2 N (0 ≦ xc2 <1,0 ≦ yc2 <1, xc2 + yc2 ≦ 1).

For example, the second lower layer LA2 includes Al _xa2 Ga _1-x2 N (0 <xa2 ≦ 1). The second doped layer LB2 includes Al _xb2 Ga _1-xb2 N (0 <xb2 <xa2). The second upper layer LC2 includes Al _xc2 Ga _1-xc2 N (0 ≦ xc2 <xb2).

  In the nitride semiconductor wafer 111, the lattice constant is set to increase along the stacking direction in the first stacked film SL1. In the first stacked film SL1, the applied stress is large in the uppermost first upper layer LC1. Further, the second lower layer LA2 (or the second strain relaxation layer LD2) is provided on the uppermost first upper layer LC1 in the first stacked film SL1. In the second lower layer LA2 (or the second strain relaxation layer LD2), the stress is once released and the strain is relaxed. In the second stacked film SL2, the lattice constant is set again to increase along the stacking direction. Thus, in each of the plurality of stacked films, the lattice constant is set to increase along the stacking direction. Thereby, generation | occurrence | production of a crack is suppressed. Then, the second doped layer LB2 is provided in the second stacked film SL2, thereby reducing the dislocation density.

  As shown in FIG. 6B, in another nitride semiconductor wafer 112 according to this embodiment, the intermediate layer 55 includes the third laminated film SL3 (the third lower layer LA3, the third doped layer LB3, and the third laminated layer SL3). It further includes a third upper layer LC3). Also in this case, the intermediate layer 55 (third stacked film SL3) can further include a third strain relaxation layer LD2. The third strain relaxation layer LD3 is provided between the second upper layer LC2 and the third lower layer LA3. The third strain relaxation layer LD3 includes a nitride semiconductor having a lattice constant smaller than that of the third lower layer LA3. The third strain relaxation layer LD3 may be regarded as the portion of the third lower layer LA3 closest to the silicon substrate 50.

FIG. 7A and FIG. 7B are schematic cross-sectional views illustrating the configuration of another nitride semiconductor wafer according to the first embodiment.
As shown in FIG. 7A, in another nitride semiconductor wafer 113 according to this embodiment, the intermediate layer 55 includes the fourth stacked film SL4 (fourth lower layer LA4, fourth doped layer LB4, and A fourth upper layer LC4) is further included. Also in this case, the intermediate layer 55 (fourth stacked film SL4) can further include a fourth strain relaxation layer LD4. The fourth strain relaxation layer LD4 is provided between the third upper layer LC3 and the fourth lower layer LA4. The fourth strain relaxation layer LD4 includes a nitride semiconductor having a lattice constant smaller than that of the fourth lower layer LA4. The fourth strain relaxation layer LD4 may be regarded as the portion of the fourth lower layer LA4 closest to the silicon substrate 50.

As described above, the intermediate layer 55 may be provided with a plurality of stacked films (for example, the first to fourth stacked films SL1 to SL4).
For example, as illustrated in FIG. 7B, in another nitride semiconductor wafer 114 according to this embodiment, the intermediate layer 55 includes the first stacked film SL1 to the nth stacked film SLn (n is 2 or more). Which is an integer). The nth stacked film SLn includes an nth lower layer LAn, an nth doped layer LBn, and an nth upper layer LCn. The nth lower layer LAn is provided on the (n−1) th upper layer LC (n−1). The nth lower layer includes a nitride semiconductor having a lattice constant smaller than that of the (n−1) th upper layer LC (n−1). The nth doped layer LBn is provided on the nth lower layer LAn. The nth doped layer LBn has a lattice constant greater than or equal to the lattice constant of the nth lower layer LAn. The n-th doped layer LBn includes a nitride semiconductor containing impurities at a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ . The nth upper layer LCn is provided on the nth doped layer LBn. The n-th upper layer LCn includes a nitride semiconductor having a lattice constant greater than or equal to the lattice constant of the n-th doped layer LBn and larger than the lattice constant of the n-th lower layer LAn.

  As described above, the intermediate layer 55 can further include the n-th stacked film SLn provided between the (n−1) -th stacked film SL (n−1) and the upper strain relaxation layer 52. The nth stacked film SLn includes an nth lower layer LAn, an nth doped layer LBn, and an nth upper layer LCn.

The intermediate layer 55 (nth stacked film SLn) can further include an nth strain relaxation layer LDn. The nth strain relaxation layer LDn is provided between the (n−1) th upper layer LC (n−1) and the nth lower layer LAn. The nth strain relaxation layer LDn includes a nitride semiconductor having a lattice constant smaller than that of the nth lower layer LAn. The n-th strain relaxing layer _{LDn, Al zn Ga 1-zn} N (0 <zn ≦ 1) is used. An AlN layer is used for the nth strain relaxation layer LDn. When the nth strain relaxation layer LDn includes AlGaN, the Al composition ratio is higher than, for example, the Al composition ratio in the nth lower layer LAn. The nth strain relaxation layer LDn may be regarded as the portion of the nth lower layer LAn that is closest to the silicon substrate 50.

For example, the n-th lower layer LAn includes Al _xan In _yan Ga _1-xan-yan N (0 ≦ xan <1, 0 <yan ≦ 1, xan + yan ≦ 1). The n-doped layer LBn _{includes Al xbn In ybn Ga 1-xbn} -ybn N (0 ≦ xbn <1,0 ≦ ybn <1, xbn + ybn ≦ 1). The n-th upper layer LCn includes Al _xcn In _ycn Ga _1-xcn-ycn N (0 ≦ xcn <1, 0 ≦ ycn <1, xcn + ycn ≦ 1).

For example, the nth lower layer LAn includes Al _xan Ga _1-xn N (0 <xn1 ≦ 1). The n-th doped layer LBn includes Al _xbn Ga _1-xbn N (0 <xbn <xan). The n-th upper layer LCn includes Al _xcn Ga _1-xcn N (0 ≦ xcn <xbn).

  In the nitride semiconductor wafer 114, the lattice constant is set to increase along the stacking direction in the (n−1) th stacked film SL (n−1). In the uppermost (n-1) upper layer LC (n-1) of the (n-1) th laminated films SL (n-1), the applied stress is large. Further, on the uppermost (n−1) upper layer LC (n−1) in the (n−1) th stacked film SL (n−1), the nth lower layer LAn (or the first layer) An n strain relaxation layer LDn) is provided. In the n-th lower layer LAn (or the n-th strain relaxation layer LDn), the stress is once released and the strain is relaxed. In the n-th stacked film SLn, the lattice constant is set again to increase along the stacking direction. Thus, in each of the plurality of stacked films, the lattice constant is set to increase along the stacking direction. Thereby, generation | occurrence | production of a crack is suppressed. The n-th doped layer LBn is provided in the n-th stacked film SLn, thereby reducing the dislocation density.

FIG. 8A and FIG. 8B are graphs illustrating the configuration of the nitride semiconductor crystal according to the first embodiment.
FIG. 8A shows an impurity concentration profile in the nitride semiconductor wafer 115a in which the intermediate layer 55 has five stacked films (first to fifth stacked films SL1 to SL5). In this example, the impurity of the doped layer is Si. The vertical axis | shaft of Fig.8 (a) is the impurity concentration C (Si) of Si. FIG. 8B shows an impurity concentration profile in the nitride semiconductor wafer 112a in which the intermediate layer 55 has three stacked films (first to third stacked films SL1 to SL3). In this example, the impurity of the doped layer is Mg. The vertical axis in FIG. 8B is the Mg impurity concentration C (Mg).

As shown in FIG. 8A, in the nitride semiconductor wafer 115a, the impurity concentration C (Si) in the doped layer (first to fifth doped layers LB1 to LB5) of the intermediate layer 55 is about 6 × 10. ^{It is 19} cm ⁻³ or more and about 9 × 10 ¹⁹ cm ⁻³ or less.

As shown in FIG. 8B, in the nitride semiconductor wafer 112a, the impurity concentration C (Mg) in the doped layer (first to third doped layers LB1 to LB3) of the intermediate layer 55 is about 4 × 10. ^{It is 19} cm ⁻³ or more and about 6 × 10 ¹⁹ cm ⁻³ or less.

  According to the nitride semiconductor wafers 115a and 112a, a nitride semiconductor wafer formed on a silicon substrate with few dislocations and cracks can be provided.

(Second Embodiment)
The present embodiment relates to a method for growing a nitride semiconductor crystal. This growth method is applied to growth of a nitride semiconductor crystal used for, for example, a semiconductor light emitting element, a semiconductor light receiving element, and an electronic device.

FIG. 9 is a flowchart illustrating the method for growing a nitride semiconductor crystal according to the second embodiment.
As shown in FIG. 9, in the nitride semiconductor crystal growth method according to this embodiment, the lower strain relaxation layer 51 is formed on the main surface 50a of the silicon substrate 50 (step S110).

Further, the intermediate layer 55 is formed (step S120). The intermediate layer 55 is formed by forming the first lower layer LA1 on the lower strain relaxation layer 51 (step S120a1) and forming the first doped layer LB1 on the first lower layer LA1 (step S120b1). ), Forming a first upper layer LC1 on the first doped layer LB1 (step S120c1). As already described, the first lower layer LA1 includes a nitride semiconductor having a lattice constant larger than that of the lower strain relaxation layer. The first doped layer LB1 is a nitride semiconductor having a lattice constant greater than or equal to that of the first lower layer LA1 and containing impurities at a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ^−3. Including. The first upper layer LC1 includes a nitride semiconductor having a lattice constant greater than or equal to the lattice constant of the first doped layer LB1 and larger than the lattice constant of the first lower layer LA1. Thus, the formation of the intermediate layer 55 includes the formation of the first stacked film SL1.

  Further, in this growth method, the upper strain relaxation layer 52 including the nitride semiconductor layer is formed on the intermediate layer 55 (step S130). Further, the functional layer 40 including a nitride semiconductor is formed on the upper strain relaxation layer 52.

  According to the present embodiment, a method for growing a nitride semiconductor crystal formed on a silicon substrate with few dislocations and cracks can be provided. That is, it is possible to provide a growth method in which the dislocation density and the crack density are simultaneously reduced.

  Also in the present embodiment, the composition ratio of the first doped layer LB1 can be different from the composition ratio of the first upper layer LC1 unlike the composition of the first lower layer LA1. That is, the lattice constant of the first doped layer LB1 is larger than the lattice constant of the first lower layer LA1 and smaller than the lattice constant of the first upper layer LC1.

For example, the first lower layer LA1 includes Al _xa1 In _ya1 Ga _1-xa1-ya1 N (0 ≦ xa1 <1, 0 ≦ ya1 <1, xa1 + ya ≦ 1). The first doped layer LB1 includes Al _xb1 In _yb1 Ga _1-xb1-yb1 N (0 ≦ xb1 <1, 0 ≦ yb1 <1, xb1 + yb1 ≦ 1). The first upper layer LC1 includes Al _xc1 In _yc1 Ga _1-xc1-yc1 N (0 ≦ xc1 <1, 0 ≦ yc1 <1, xc1 + yc1 ≦ 1).

For example, the first lower layer LA1 includes Al _xa1 Ga _1-xa N (0 <xa1 ≦ 1). The first doped layer LB1 includes Al _xb1 Ga _1-xb1 N (0 <xb1 <xa1). The first upper layer LC1 includes Al _xc1 Ga _1-xc1 N (0 ≦ xc1 <xb1).

The lower strain relaxation layer 51 is, for example, AlN. The upper strain relaxation layer is, for example, Al _z0 Ga _1-z0 N (0 <z0 ≦ 1).

  The impurity contained in the first doped layer LB1 is, for example, at least one of Si, Mg, Mn, Fe, O, and C. The thickness of the first doped layer LB1 is 20 nm or more and 150 nm or less.

The formation of the intermediate layer 55 may include the formation of a plurality of stacked films.
FIG. 10 is a flowchart illustrating the method for growing a nitride semiconductor crystal according to the second embodiment.
As shown in FIG. 10, the formation of the intermediate layer 55 (step S120) forms the second lower layer LA2 on the first upper layer LC1 (step S120a2), and on the second lower layer LA2. The method further includes forming the second doped layer LB2 (Step S120b2) and forming the second upper layer LC2 on the second doped layer LB2 (Step S120c2). As already described, the second lower layer LA2 includes a nitride semiconductor having a lattice constant smaller than that of the first upper layer LC1. The second doped layer LB2 is made of a nitride semiconductor having a lattice constant greater than or equal to that of the second lower layer LA2 and containing impurities at a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ^−3. Including. The second upper layer LC2 includes a nitride semiconductor having a lattice constant greater than or equal to the lattice constant of the second doped layer LB2 and larger than the lattice constant of the second lower layer LA2.

As shown in FIG. 10, the formation of the intermediate layer 55 further includes forming a second strain relaxation layer LD2 provided between the first upper layer LC1 and the second lower layer LA2 (Step S120d2). Can be included. The second strain relaxation layer LD2 includes a nitride semiconductor having a lattice constant smaller than that of the second lower layer LA2. For example, Al _z2 Ga _1-z2 N (0 <z2 ≦ 1) is formed as the second strain relaxation layer LD2.

Second lower layer LA2 _{includes Al xa2 In ya2 Ga 1-xa2} -ya2 N (0 ≦ xa2 <1,0 ≦ ya2 <1, xa2 + ya2 ≦ 1). The second doped layer LB2 includes Al _xb2 In _yb2 Ga _1-xb2-yb2 N (0 ≦ xb2 <1, 0 ≦ yb2 <1, xb2 + yb2 ≦ 1). Second upper layer LC2 _{includes Al xc2 In yc2 Ga 1-xc2} -yc2 N (0 ≦ xc2 <1,0 ≦ yc2 <1, xc2 + yc2 ≦ 1).

For example, the second lower layer LA2 includes Al _xa2 Ga _1-x2 N (0 <xa2 ≦ 1). The second doped layer LB2 includes Al _xb2 Ga _1-xb2 N (0 <xb2 <xa2). The second upper layer LC2 includes Al _xc2 Ga _1-xc2 N (0 ≦ xc2 <xb2).

  Thus, in the growth method according to the present embodiment, the formation of the intermediate layer 55 includes forming a plurality of stacked films.

(Third embodiment)
The third embodiment relates to a nitride semiconductor device.
The nitride semiconductor device according to the embodiment includes, for example, a semiconductor light emitting element, a semiconductor light receiving element, and an electronic device. The nitride semiconductor device according to the embodiment can be manufactured based on the wafer according to the first embodiment.

FIG. 11 is a schematic cross-sectional view illustrating the configuration of a nitride semiconductor device according to the third embodiment.
As shown in FIG. 11, the nitride semiconductor device 210 according to this embodiment includes an intermediate layer 55 that is formed on the main surface 50 a of the silicon substrate 50 and includes a nitride semiconductor, and a nitride layer provided on the intermediate layer 55. An upper strain relaxation layer 52 including a physical semiconductor layer, and a functional layer 40 provided on the upper strain relaxation layer 52 and including a nitride semiconductor. The intermediate layer 55 includes a first lower layer LA1, a first doped layer LB1, and a first upper layer LC1. The first lower layer LA1 is formed on the main surface 50a of the silicon substrate 50 and includes a nitride semiconductor. The first doped layer LB1 is provided on the first lower layer LA1. The first doped layer LB1 has a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the first lower layer LB1 and contains impurities at a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ^−3. Including nitride semiconductors. The first upper layer LC1 is provided on the first doped layer LB1. The first upper layer LC1 includes a nitride semiconductor having a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the first doped layer LB1 and larger than the lattice constant of the nitride semiconductor of the first lower layer LA1.

  In this example, the nitride semiconductor device 210 further includes a lower strain relaxation layer 51. The lower strain relaxation layer 51 is provided between the silicon substrate 50 and the first lower layer LA1. The lattice constant of the lower strain relaxation layer 51 is smaller than the lattice constant of the first lower layer LA1.

  In this example, the nitride semiconductor device 210 further includes a silicon substrate 50. However, the embodiment is not limited to this. After the intermediate layer 55, the upper strain relaxation layer 52, and the functional layer 40 are formed on the silicon substrate 50, the silicon substrate 50 may be removed. At this time, for example, at least a part of the lower strain relaxation layer 51 may be removed.

  In this example, the functional layer 40 is provided on the upper strain relaxation layer 52 and is provided on the first semiconductor layer 10 including the nitride semiconductor and having the first conductivity type (for example, n-type) and the first semiconductor layer 10. A second semiconductor layer 20 including a nitride semiconductor and having a second conductivity type (for example, p-type) different from the first conductivity type, and a light emitting portion provided between the first semiconductor layer 10 and the second semiconductor layer 20 30. The light emitting unit 30 includes, for example, a plurality of barrier layers 31 and a well layer 32 provided between the plurality of barrier layers 31.

  The nitride semiconductor device 210 is a semiconductor light emitting element. More specifically, the nitride semiconductor device 210 is an LED (Light Emitting Diode).

  In the nitride semiconductor device 210, the light emitting unit 30 is provided on a part of the first semiconductor layer 10, and the second semiconductor layer 20 is provided on the light emitting unit 30. A first electrode 10 e is provided on the first semiconductor layer 10, and a second electrode 20 e is provided on the second semiconductor layer 20. When a voltage is applied between the first electrode 10 e and the second electrode 20 e, holes and electrons are recombined in the light emitting unit 30, and light is emitted from the light emitting unit 30. This light is extracted from the surface on the second semiconductor layer 20 side as viewed from the light emitting unit 30 or from the surface on the first semiconductor layer 10 side as viewed from the light emitting unit 30.

  According to the nitride semiconductor device 210, a nitride semiconductor device formed on a silicon substrate with few dislocations and cracks can be provided. For example, the light emission efficiency is improved by reducing the dislocation density and reducing the number of cracks. Furthermore, reliability can be improved.

FIG. 12 is a schematic cross-sectional view illustrating the configuration of another nitride semiconductor device according to the third embodiment.
As illustrated in FIG. 12, another nitride semiconductor device 220 according to the embodiment also includes the intermediate layer 55, the upper strain relaxation layer 52, and the functional layer 40. In this example, the functional layer 40 includes a first semiconductor layer 71 provided on the upper strain relaxation layer 52 and a second semiconductor layer 72 provided on the first semiconductor layer 71. The band gap energy of the second semiconductor layer 72 is larger than the band gap energy of the first semiconductor layer 71.

  The first semiconductor layer 71 becomes a channel layer. The second semiconductor layer 72 becomes a barrier layer. The second semiconductor layer 72 is in a heterojunction with the first semiconductor layer 71. The intermediate layer 55, the upper strain relief layer 52, the first semiconductor layer 71, and the second semiconductor layer 72 are epitaxially grown on the main surface of the silicon substrate 50 in this order.

The first semiconductor layer 71 includes, for example, undoped Al _α Ga _1-α N (0 ≦ α ≦ 1) that does not contain impurities. The second semiconductor layer 72 includes, for example, _{Al β Ga 1-β N (} 0 ≦ β ≦ 1, α <β) of undoped or n-type a. For example, an undoped GaN layer is used for the first semiconductor layer 71, and an undoped or n-type AlGaN layer is used for the second semiconductor layer 72. For the upper strain relaxation layer 52, for example, an AlN layer or an AlGaN layer is used.

  A source electrode 73 and a drain electrode 74 are provided on the second semiconductor layer 72 so as to be separated from each other. Each of the source electrode 73 and the drain electrode 74 is in ohmic contact with the surface of the second semiconductor layer 72. A gate electrode 75 is provided on the second semiconductor layer 72 between the source electrode 73 and the drain electrode 74. The gate electrode 75 is in Schottky contact with the surface of the second semiconductor layer 72.

  The lattice constant of the second semiconductor layer 72 is smaller than the lattice constant of the first semiconductor layer 71. As a result, distortion occurs in the second semiconductor layer 72, and piezoelectric polarization occurs in the second semiconductor layer 72 due to the piezoelectric effect. Thereby, a two-dimensional electron gas 71g is formed in the vicinity of the interface between the first semiconductor layer 71 and the second semiconductor layer 72.

  In the nitride semiconductor device 220, by controlling the gate voltage applied to the gate electrode 75, the concentration of the two-dimensional electron gas 71 g below the gate electrode 75 increases and decreases and flows between the source electrode 73 and the drain electrode 74. The current is controlled. The nitride semiconductor device 220 is a HEMT (High Electron Mobility Transistor).

  According to the nitride semiconductor device 220, a nitride semiconductor device formed on a silicon substrate with few dislocations and cracks can be provided. Since the dislocation density is reduced and cracks are reduced, the performance is stabilized and the reliability can be improved.

  In the embodiment, the semiconductor layer is grown by, for example, metal-organic chemical vapor deposition (MOCVD) method, metal-organic vapor phase epitaxy (MOVPE) method, molecular beam epitaxy. (Molecular Beam Epitaxy: MBE) method, halide vapor phase epitaxy method (HVPE) method and the like can be used.

For example, when the MOCVD method or the MOVPE method is used, the following can be used as raw materials for forming each semiconductor layer. For example, TMGa (trimethyl gallium) and TEGa (triethyl gallium) can be used as the Ga raw material. For example, TMIn (trimethylindium), TEIn (triethylindium), or the like can be used as the In material. As a raw material for Al, for example, TMAl (trimethylaluminum) can be used. As a raw material of N, for example, NH ₃ (ammonia), MMHy (monomethylhydrazine), DMHy (dimethylhydrazine) and the like can be used.

For example, the following can be used as the impurity source. For example, silane (SiH ₄ ) can be used as the Si source gas. As a raw material of Mg, for example, biscyclopentadienyl magnesium (Cp ₂ Mg) can be used. For example, tricarbonyl manganese (MMT) can be used as a raw material of Mn. For example, iron carbonyl (Fe (CO) ₅ ) or ferrocene (Cp ₂ Fe) can be used as a raw material for Fe. As a raw material for oxygen (O), for example, oxygen plasma can be used.

  According to the embodiments, a nitride semiconductor wafer, a nitride semiconductor device, and a method for growing a nitride semiconductor crystal, which are formed on a silicon substrate and have few dislocations and cracks, are provided.

In this specification, “nitride semiconductor” means B _x In _y Al _z Ga _1-xyz N (0 ≦ x ≦ 1, 0 ≦ y ≦ 1, 0 ≦ z ≦ 1, x + y + z ≦ 1) Semiconductors having all compositions in which the composition ratios x, y, and z are changed within the respective ranges are included. Furthermore, in the above chemical formula, those further containing a group V element other than N (nitrogen), those further containing various elements added for controlling various physical properties such as conductivity type, and unintentionally Those further including various elements included are also included in the “nitride semiconductor”.

  In the present specification, “vertical” and “parallel” include not only strict vertical and strict parallel but also include, for example, variations in the manufacturing process, and may be substantially vertical and substantially parallel. It ’s fine.

The embodiments of the present invention have been described above with reference to specific examples. However, embodiments of the present invention are not limited to these specific examples. For example, specific elements such as a silicon substrate, a lower strain relaxation layer, an intermediate layer, an upper strain relaxation layer, a functional layer, a lower layer, a doped layer, and an upper layer included in a nitride semiconductor wafer or a nitride semiconductor device With respect to such configurations, those skilled in the art can appropriately select from the well-known ranges to implement the present invention in the same manner, and are included in the scope of the present invention as long as similar effects can be obtained.
Moreover, what combined any two or more elements of each specific example in the technically possible range is also included in the scope of the present invention as long as the gist of the present invention is included.

  In addition, all nitride semiconductor wafers that can be implemented by those skilled in the art by appropriately modifying the design based on the nitride semiconductor wafer, nitride semiconductor device, and nitride semiconductor crystal growth method described above as embodiments of the present invention. A nitride semiconductor device and a method for growing a nitride semiconductor crystal also belong to the scope of the present invention as long as they include the gist of the present invention.

  In addition, in the category of the idea of the present invention, those skilled in the art can conceive of various changes and modifications, and it is understood that these changes and modifications also belong to the scope of the present invention. .

  Although several embodiments of the present invention have been described, these embodiments are presented by way of example and are not intended to limit the scope of the invention. These novel embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the scope of the invention. These embodiments and modifications thereof are included in the scope and gist of the invention, and are included in the invention described in the claims and the equivalents thereof.

  DESCRIPTION OF SYMBOLS 10 ... 1st semiconductor layer, 10e ... 1st electrode, 20 ... 2nd semiconductor layer, 20e ... 2nd electrode, 30 ... Light emission part, 31 ... Barrier layer, 32 ... Well layer, 40 ... Functional layer, 50 ... Silicon substrate 50a ... main surface, 51 ... lower strain relaxation layer, 52 ... upper strain relaxation layer, 55 ... intermediate layer, 71 ... first semiconductor layer, 71g ... two-dimensional electron gas, 72 ... second semiconductor layer, 73 ... sheath Electrode, 74 ... Drain electrode, 75 ... Gate electrode, 110, 111, 112, 112a, 113, 114, 115a ... Nitride semiconductor wafer, 210, 220 ... Nitride semiconductor device, C (Mg), C (Si) ... Impurity concentration, EDD: edge dislocation density, LA1 to LA4: first to fourth lower layers, LAn: nth lower layer, LA (n-1) ... (n-1) lower layer, LB1 LB4 ... 1st to 4th door LBn ... n-th doped layer, LB (n-1) ... (n-1) -doped layer, LC1-LC4 ... first-fourth upper layer, LCn ... n-th upper layer, LC (n- 1) ... (n-1) upper layer, LD2 to LD4 ... 2nd to 4th lower layer, LDn ... nth strain relaxation layer, LD (n-1) ... (n-1) strain relaxation layer, S01 to S04: First to fourth samples, SDD: Spiral dislocation density, SL1 to SL4: First to fourth stacked films, SLn: Nth stacked film, SL (n-1): (n-1) stacked layers film

Claims (8)

A silicon substrate;
A lower strain relaxation layer including a nitride semiconductor layer provided on the main surface of the silicon substrate;
An intermediate layer provided on the lower strain relaxation layer and including a nitride semiconductor;
An upper strain relaxation layer including a nitride semiconductor layer provided on the intermediate layer;
A functional layer including a nitride semiconductor provided on the upper strain relaxation layer;
With
The intermediate layer is
A first lower layer having a thickness of not less than 100 nm and not more than 500 nm including a nitride semiconductor provided on the lower strain relaxation layer and having a lattice constant larger than that of the nitride semiconductor of the lower strain relaxation layer When,
It is provided on the first lower layer and has a lattice constant equal to or higher than the lattice constant of the nitride semiconductor of the first lower layer and is not less than 1 × 10 ¹⁸ cm ^{−3 and} less than 1 × 10 ²¹ cm ⁻³ . The concentration is higher than that of the first lower layer and includes at least one of silicon (Si), magnesium (Mg), manganese (Mn), iron (Fe), oxygen (O), and carbon (C). A first doped layer having a thickness of 20 nm or more and 150 nm or less, including a nitride semiconductor containing impurities;
Nitriding provided on the first doped layer and having a lattice constant that is greater than or equal to the lattice constant of the nitride semiconductor of the first doped layer and greater than the lattice constant of the nitride semiconductor of the first lower layer A first upper layer having a thickness of 100 nm or more and 500 nm or less , including a physical semiconductor;
Nitride semiconductor wafer containing. The composition ratio of the first doped layer is different from the composition of the first upper layer, unlike the composition of the first lower layer,
The nitride semiconductor wafer according to claim 1, wherein the lattice constant of the first doped layer is larger than the lattice constant of the first lower layer and smaller than the lattice constant of the first upper layer. The intermediate layer is
A second lower layer including a nitride semiconductor provided on the first upper layer and having a lattice constant smaller than the lattice constant of the nitride semiconductor of the first upper layer;
It is provided on the second lower layer and has a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the second lower layer and is not less than 1 × 10 ¹⁸ cm ^{−3 and} less than 1 × 10 ²¹ cm ⁻³ . A second doped layer comprising a nitride semiconductor having a concentration and containing impurities at a higher concentration than the second lower layer;
Nitriding provided on the second doped layer and having a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the second doped layer and greater than the lattice constant of the nitride semiconductor of the second lower layer A second upper layer containing a physical semiconductor;
The nitride semiconductor wafer according to claim 1 or 2 further comprising a. The intermediate layer is
A second strain relaxation layer including a nitride semiconductor provided between the first upper layer and the second lower layer and having a lattice constant smaller than that of the nitride semiconductor of the second lower layer; 4. The nitride semiconductor wafer according to claim 3, further comprising: The first lower layer includes Al _xa1 Ga _1-xa N (0 <xa1 ≦ 1),
The first doped layer includes Al _xb1 Ga _1-xb1 N (0 <xb1 <xa1),
The first upper _layer, Al _{xc1 Ga 1-xc1} N nitride semiconductor wafer according to any one of claims 1-4 comprising (0 ≦ xc1 <xb1). An intermediate layer formed on the main surface of the silicon substrate and including a nitride semiconductor;
An upper strain relaxation layer including a nitride semiconductor layer provided on the intermediate layer;
A functional layer including a nitride semiconductor provided on the upper strain relaxation layer;
With
The intermediate layer is
A first lower layer having a thickness of not less than 100 nm and not more than 500 nm including a nitride semiconductor formed on the main surface;
A concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ⁻³ provided on the first lower layer and having a lattice constant greater than or equal to that of the nitride semiconductor of the first lower layer; An impurity containing at least one of silicon (Si), magnesium (Mg), manganese (Mn), iron (Fe), oxygen (O), and carbon (C) at a higher concentration than the first lower layer A first doped layer having a thickness of 20 nm to 150 nm including a nitride semiconductor containing
Nitriding provided on the first doped layer and having a lattice constant that is greater than or equal to the lattice constant of the nitride semiconductor of the first doped layer and greater than the lattice constant of the nitride semiconductor of the first lower layer A first upper layer having a thickness of 100 nm or more and 500 nm or less , including a physical semiconductor;
A nitride semiconductor device comprising: The functional layer is
A first semiconductor layer of a first conductivity type including a nitride semiconductor provided on the upper strain relaxation layer;
A second semiconductor layer of a second conductivity type provided on the first semiconductor layer and including a nitride semiconductor and different from the first conductivity type;
A light emitting unit provided between the first semiconductor layer and the second semiconductor layer and including a plurality of barrier layers and a well layer provided between the plurality of barrier layers;
The nitride semiconductor device according to claim 6 comprising: Forming a lower strain relaxation layer including a nitride semiconductor on the main surface of the silicon substrate;
A first lower layer having a thickness of 100 nm to 500 nm including a nitride semiconductor having a lattice constant larger than that of the nitride semiconductor of the lower strain relaxation layer is formed on the lower strain relaxation layer. And
The first lower layer has a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the first lower layer, and has a concentration of 1 × 10 ¹⁸ cm ⁻³ or more and less than 1 × 10 ²¹ cm ^−3. Contains impurities including at least one of silicon (Si), magnesium (Mg), manganese (Mn), iron (Fe), oxygen (O), and carbon (C) at a higher concentration than the first lower layer. Forming a first doped layer including a nitride semiconductor and having a thickness of 20 nm to 150 nm ;
A nitride semiconductor having a lattice constant greater than or equal to the lattice constant of the nitride semiconductor of the first doped layer and greater than the lattice constant of the nitride semiconductor of the first lower layer on the first doped layer Forming a first upper layer having a thickness of not less than 100 nm and not more than 500 nm, and forming an intermediate layer ,
Forming an upper strain relaxation layer including a nitride semiconductor layer on the intermediate layer;
A method for growing a nitride semiconductor crystal, wherein a functional layer containing a nitride semiconductor is formed on the upper strain relaxation layer.