JP2006210660A - Manufacturing method of semiconductor substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a semiconductor substrate manufacturing method for forming a nitride semiconductor film on a silicon substrate or the like.
SOLUTION: The step of implanting ions near the surface of a first nitride semiconductor substrate 11 and the step of superposing the surface side of the first nitride semiconductor substrate 11 on a second substrate 2 A manufacturing process including a step of heat-treating two substrates 11 and 2 and a step of peeling most of the first nitride semiconductor substrate 11 from the second substrate 2 with the ion-implanted layer 12 (13) as a boundary. Is the method.
[Selection] Figure 1

Description

  The present invention relates to a semiconductor substrate manufacturing method and a semiconductor substrate for forming a nitride semiconductor thin film on a silicon substrate or the like.

  Nitride semiconductors composed of indium, gallium, aluminum, and nitrogen are used as innovative high-efficiency light-emitting device materials that cover most regions from ultraviolet to visible light by controlling the composition ratio of group III elements. Development is in progress and put to practical use.

  Nitride semiconductors also have high saturation electron velocities and high breakdown voltage, so they are expected to be applied as materials for electronic devices that realize orders of magnitude higher efficiency and higher output in the high frequency range in the future. .

  When forming a nitride semiconductor as a thin film, the biggest problem is the selection of the substrate. Conventionally, it has been extremely difficult to manufacture a single crystal nitride semiconductor itself, and it has been almost impossible to obtain it. For this reason, nitride semiconductor devices such as blue LEDs have usually been formed on sapphire substrates, silicon carbide substrates and the like.

  However, sapphire and silicon carbide differ from nitride semiconductors in crystal systems, lattice constants, thermal expansion coefficients, and the like. For this reason, dislocations and defects are introduced at a high density in a nitride semiconductor thin film formed on a sapphire substrate, a silicon carbide substrate, etc., and the defects in these crystals cause the device characteristics to deteriorate over time. It was.

  Recently, a method has been developed in which a GaN film is formed thick on the sapphire substrate by HVPE (hydride vapor phase epitaxy) and the GaN film is peeled off from the sapphire substrate. This method has made it possible to produce a single crystal nitride semiconductor substrate having a low dislocation density, which has been extremely difficult in the past.

  When this single crystal nitride semiconductor is used as a substrate for thin film growth, the number of crystal defects in the thin film including the device structure is reduced, so that a nitride semiconductor device having excellent characteristics such as high light emission intensity and long device life can be produced. Is possible.

  The prior art document information related to the invention of this application includes the following.

Japanese Patent Laid-Open No. 10-321548 Japanese Patent Laid-Open No. 11-40786 JP 11-297583 A

  However, a GaN substrate grown by the HVPE method has an extremely long time for manufacturing per substrate, and therefore the unit price is much higher than that of a sapphire substrate or the like. That is, the single crystal nitride semiconductor substrate has a problem that the cost is extremely high, and at present, it is practically impossible to apply to a blue LED or a high-frequency electronic device that requires a low price. .

  Accordingly, an object of the present invention is to provide a semiconductor substrate manufacturing method for forming a low dislocation density nitride semiconductor thin film on a silicon substrate or a substrate made of an arbitrary material.

  The present invention has been made to achieve the above object, and the invention of claim 1 includes a step of implanting ions in the vicinity of the surface of the first nitride semiconductor substrate, and the first nitride semiconductor substrate. A step of superimposing the surface side of the first nitride semiconductor substrate on the second substrate, a step of heat-treating the two superimposed substrates, and a portion of the first nitride semiconductor substrate on the boundary of the ion-implanted layer. 2 is a method for manufacturing a semiconductor substrate, including a step of peeling off from the substrate.

  The invention of claim 2 includes a step of implanting ions in the vicinity of the surface of the first nitride semiconductor substrate, a step of heat-treating the first nitride semiconductor substrate, and a surface side of the first nitride semiconductor substrate. Is a method of manufacturing a semiconductor substrate, including a step of bonding the first nitride semiconductor substrate to the second substrate and a step of peeling most of the first nitride semiconductor substrate from the second substrate with the ion-implanted layer as a boundary. .

  According to a third aspect of the present invention, after most of the first nitride semiconductor substrate is peeled off, the ion-implanted layer is removed and reused as the first nitride semiconductor substrate. 2. A method for producing a semiconductor substrate according to 2.

  The invention of claim 4 is the method for manufacturing a semiconductor substrate according to any one of claims 1 to 3, wherein the first nitride semiconductor substrate is made of wurtzite GaN or wurtzite AlN.

  The invention of claim 5 is the method for manufacturing a semiconductor substrate according to any one of claims 1 to 4, wherein the surface of the first nitride semiconductor substrate is a (000-1) nitrogen surface.

  According to a sixth aspect of the present invention, the surface of the first nitride semiconductor substrate is a surface that is off-cut within a range from 0 ° to less than 8 ° in an arbitrary direction from the (000-1) nitrogen surface. A method for producing a semiconductor substrate according to any one of?

  A seventh aspect of the present invention is the method for manufacturing a semiconductor substrate according to any one of the first to sixth aspects, wherein the ions comprise one or more ions of hydrogen, nitrogen, oxygen, neon, and argon. .

  The invention according to claim 8 is the method for manufacturing a semiconductor substrate according to any one of claims 1 to 7, wherein the second substrate is made of any one of silicon, glass, and metal.

  The invention according to claim 9 is the method for manufacturing a semiconductor substrate according to any one of claims 1 to 8, wherein the first nitride semiconductor substrate has a thickness of about 400 μm.

  The invention according to claim 10 is the semiconductor substrate according to any one of claims 1 to 9, wherein the ion implantation is performed so as to have a concentration peak at a depth of 2 μm or less from the surface of the first nitride semiconductor substrate. It is a manufacturing method.

  According to an eleventh aspect of the present invention, the heat treatment is performed at a temperature of 800 ° C. or higher in a gas atmosphere composed of a single gas of hydrogen, nitrogen, ammonia, oxygen, argon, neon, or helium, or a mixed gas thereof. It is a manufacturing method of the semiconductor substrate in any one of Claims 1-10 performed more than time.

  According to the present invention, the nitride semiconductor thin film having a low dislocation density can be formed on a silicon substrate or a substrate made of any material at a low manufacturing cost.

  DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the accompanying drawings.

  First, a semiconductor substrate manufactured using the manufacturing method according to this embodiment will be described with reference to FIG.

  As shown in FIG. 2E, a semiconductor substrate (semiconductor wafer or template substrate) 1 according to the present embodiment has a single crystal of low dislocation density on a single crystal silicon substrate 2 as a second substrate. A GaN thin film 3 is formed as a nitride semiconductor thin film. As will be described later, the semiconductor substrate 1 is used as a substrate for a blue LED or a high-frequency electronic device (for example, a high-frequency transistor).

  As the second substrate, a substrate made of glass or metal may be used. The nitride semiconductor thin film may be made of indium, gallium, aluminum, and nitrogen (for example, an AlN thin film).

  Next, a method for manufacturing the semiconductor substrate 1 will be described with reference to FIGS.

  FIG. 1A to FIG. 1D are cross-sectional views showing a part of a semiconductor substrate manufacturing process (processes until heat treatment) according to a preferred embodiment of the present invention. 2A to 2E are cross-sectional views showing a part of the semiconductor substrate manufacturing process (process after heat treatment) according to a preferred embodiment of the present invention.

  First, as shown in FIG. 1A, a single crystal GaN substrate 11 (thickness d) having a low dislocation density is prepared as a first nitride semiconductor substrate. This GaN substrate 11 is made of wurtzite GaN, and is arranged so that the front side is a (000-1) nitrogen surface and the back side is a (0001) gallium surface.

  As shown in FIG. 1B, ions are implanted from above into the vicinity of the surface of the GaN substrate 11 to form an ion implantation layer 12 at a depth of about several μm from the surface of the GaN substrate 11. As the ions to be implanted, those composed of one or more ions of hydrogen, nitrogen, oxygen, neon, and argon are used. In this embodiment, hydrogen and nitrogen ions are used as ions to be implanted. At this time, a thin film 11 a to be finally obtained GaN thin film 3 (see FIG. 2E) is formed from the surface of the GaN substrate 11 to the upper surface of the ion implantation layer 12.

  As shown in FIG. 1 (c), a single crystal silicon substrate 2 is prepared, and the surface side of the GaN substrate 11 is overlapped with and adhered to the surface of the silicon substrate 2. Thereafter, the two superposed GaN substrates 11 and silicon substrate 2 are heat treated and bonded together.

  Now, during this heat treatment, a large number of dangling bonds are formed in a planar shape due to defects induced by ions inside the ion implantation layer 12 formed in the GaN substrate 11. A crack layer 13 as shown in FIG. Then, a crack occurs due to thermal stress or the like along the plane of the crack layer 13, and the GaN substrate 11 is separated vertically from the crack layer 13.

  When this phenomenon is utilized, as shown in FIG. 2A, most of the GaN substrate 11 is separated from the crack layer 13 with the thin film 11a (see FIG. 1) near the surface bonded to the silicon substrate 2 being left. 11A can be peeled off from the silicon substrate 2. That is, the thin film 11 a is transferred from the GaN substrate 11 to the silicon substrate 2 and becomes the GaN thin film 3.

  Thereafter, as shown in FIG. 2B, most of the peeled GaN substrate 11 becomes a GaN substrate 21 as shown in FIG. 2C by removing the cracked layer 13. The GaN substrate 21 can be reused as the first nitride semiconductor substrate because the thickness d2 is only slightly smaller than the thickness d of the GaN substrate 11 of FIG.

  On the other hand, as shown in FIG. 2D, when the silicon substrate 2 with the GaN thin film 3 attached to the surface is subjected to further heat treatment to remove the crack layer 13, the semiconductor substrate 1 described in FIG. can get.

  The operation of the present embodiment will be described.

  In the manufacturing method according to the present embodiment, first, the ion implantation layer 12 is formed in the GaN substrate 11, and the GaN substrate 11 is overlaid on the silicon substrate 2 and bonded by heat treatment. At this time, since the ion implantation layer 12 becomes the crack layer 13, the semiconductor in which the GaN thin film 3 is formed on the silicon substrate 2 by peeling most of the GaN substrate 11 from the silicon substrate 2 with the crack layer 13 as a boundary. A substrate 1 is obtained. On the other hand, most of the GaN substrate 11 can be reused as the GaN substrate 11 because the crack layer 13 is removed to become the GaN substrate 21.

  In other words, when this manufacturing method is used, a single crystal nitride semiconductor substrate (for example, GaN substrate 11) having a problem of low dislocation density but high price is changed from a low-cost substrate (for example, silicon substrate 2). It is possible to “transfer” a large amount of a nitride semiconductor thin film having a low dislocation density (for example, GaN thin film 3) on the semiconductor substrate and to “replicate” a semiconductor substrate having a nitride semiconductor thin film having a low dislocation density in large quantities.

  In particular, a low-priced substrate may be a silicon substrate that is several orders of magnitude cheaper than a single crystal nitride semiconductor substrate. Then, the unit price per semiconductor substrate having a nitride semiconductor thin film having a low dislocation density can be drastically reduced as compared with one single crystal nitride semiconductor substrate.

  Therefore, according to the manufacturing method according to the present embodiment, a low dislocation density nitride semiconductor thin film can be formed on the silicon substrate 2 or a substrate made of an arbitrary material at a low manufacturing cost.

  In the above embodiment, the GaN substrate 11 after ion implantation and the silicon substrate 2 are overlapped, and the two substrates 11 and 2 are heat-treated and bonded. However, the GaN substrate 11 after ion implantation is heat-treated. Then, the heat-treated GaN substrate 11 may be bonded to the silicon substrate 2.

  In the above embodiment, the example in which the GaN thin film 3 is formed as the nitride semiconductor thin film has been described. However, when the AlN thin film is formed as the nitride semiconductor film, the wurtzite type is used as the first nitride semiconductor substrate. An AlN substrate made of AlN is used.

Example 1
First, a single crystal GaN substrate 11 having a low dislocation density grown by the HVPE method is prepared. The surface side of the GaN substrate 11 is arranged to be a (000-1) nitrogen surface. The thickness d of the GaN substrate 11 is about 400 μm.

  Hydrogen and nitrogen ions are implanted in the vicinity of the surface of the GaN substrate 11 by ion implantation to form an ion implantation layer 12. The ion implantation is desirably performed so as to have a concentration peak at a depth of 2 μm or less from the surface of the GaN substrate 11. In Example 1, the ion implantation energy was set to 400 keV.

  Next, a single crystal silicon substrate 2 having a plane orientation of (100) or (111) is prepared, and after cleaning the surface of the silicon substrate 2 and the ion-implanted GaN substrate 11, the surfaces are overlapped and adhered to each other. .

  The superposed substrates 11 and 2 are introduced into an annealing furnace capable of gas replacement, and bonded annealing (heat treatment) is performed in the furnace at a temperature of 800 ° C. or more for 2 hours or more, and the silicon substrate 2 and ions have been implanted. The GaN substrate 11 is bonded.

  In Example 1, the gas atmosphere in the annealing furnace was a mixed gas of hydrogen and nitrogen. As the gas atmosphere, a single gas such as hydrogen, nitrogen, ammonia, oxygen, argon, neon, helium, or a mixed gas thereof may be used.

  During the bond annealing, since the ion implantation layer 12 becomes the crack layer 13, most of the GaN substrate 11 can be peeled off from the silicon substrate 2 with the crack layer 13 as a boundary. As a result, the bonded substrates 11 and 2 are a silicon substrate in which most of the GaN substrate 11 having a thickness of about 398 μm and a GaN thin film 3 having a low dislocation density and a thickness of about 2 μm are attached to the surface. 2 and 2 are separated.

  Most of the peeled off GaN substrate 11 becomes a GaN substrate 21 (which has almost the same structure as the GaN substrate 11) by removing the cracked layer 13 by a chemical mechanical polishing method or the like. It can be used for the formation process of the GaN thin film 3 on the silicon substrate 2 by ion implantation as shown in FIG.

  This is because the state of the GaN substrate 21 is the same as that before the use of the process, except that the thickness d2 is about 0.5% thinner than the thickness d of the GaN substrate 11. That is, one GaN substrate 11 can be reused and reused ideally several tens to a hundred times.

  Although the single crystal GaN substrate 11 having a low dislocation density is expensive per sheet, the process of growing the GaN thin film 3 having a low dislocation density while reusing the single crystal GaN substrate 21 as described above is a semiconductor substrate. This has the effect of significantly reducing the manufacturing cost.

  On the other hand, when the silicon substrate 2 on which the GaN thin film 3 having a low dislocation density of about 2 μm is adhered is subjected to further heat treatment, damage caused by ion implantation and dangling bond formation is removed (the crack layer 13 is removed). It can be used as an inexpensive semiconductor substrate 1 for forming a nitride semiconductor device having excellent characteristics and reliability.

  Here, an example of a nitride semiconductor device manufactured using the semiconductor substrate 1 will be described. As specific application examples, there are a blue LED 31 as shown in FIG. 3 and a high-frequency transistor 41 as shown in FIG.

  As shown in FIG. 3, the blue LED 31 includes an n-type GaN epitaxial layer 32, a multi-quantum well layer 33 made of InGaN and GaN, and a p-type GaN epitaxial layer 34 on the semiconductor substrate 1 using the MOVPE method. After sequential epitaxial growth, a current diffusion layer 35 made of a transparent electrode is formed on the p-type GaN epitaxial layer 34, and the p-type electrode 36 is formed on the current diffusion layer 35 by a predetermined photolithography method. An n-type electrode 37 is formed on the back surface.

  This blue LED 31 has excellent characteristics such as high light emission intensity and long element lifetime because there are few crystal defects that can be non-radiative recombination centers in the device structure.

  As shown in FIG. 4, the high-frequency transistor 41 is formed by sequentially growing a semi-insulating GaN epitaxial layer 42 and an undoped AlGaN epitaxial layer 43 on the semiconductor substrate 1 using the MOVPE method, and then performing a predetermined photolithography method. The source electrode 44, the gate electrode 45, the drain electrode 46, and the SiNx passivation film 47 are formed on the undoped AlGaN epitaxial layer 43, respectively.

  The high-frequency transistor 41 has excellent characteristics such as high speed and high output because there are few crystal defects that cause electron scattering in the device structure.

(Example 2)
Using an AlN substrate made of wurtzite AlN as the first nitride semiconductor substrate, an AlN thin film was formed on the silicon substrate 2 in the same manner as in Example 1 to produce a semiconductor substrate. Also in Example 2, the same effects as in Example 1 can be obtained, and a semiconductor substrate having a low dislocation density nitride semiconductor thin film can be manufactured at low cost.

(Example 3)
Instead of the GaN substrate 11 of Example 1, a surface cut off in a range of 0 ° to less than 8 °, preferably 1 ° to less than 3 ° in any direction from the (000-1) nitrogen surface is the surface side Using the GaN substrate arranged as described above, a GaN thin film was formed on the substrate in the same manner as in Example 1 to produce a semiconductor substrate. The reason why the off cut is in the range of 0 ° or more and less than 8 ° is that when the off cut is 8 ° or more, the surface morphology (morphology) of the GaN thin film epitaxially grown on the GaN substrate is remarkably deteriorated. When a plurality of epitaxial layers are sequentially epitaxially grown on the manufactured semiconductor substrate by the MOVPE method, the morphology of each epitaxial layer is improved.

Example 4
A glass substrate or a metal substrate was used instead of the silicon substrate 2 of Example 1, and a GaN thin film 3 was formed on the substrate in the same manner as in Example 1 to produce a semiconductor substrate. As the second substrate, it is desirable to use silicon because of technical accumulation in the industrial aspect, but if a substrate made of a cheaper material such as glass or metal is used as in the fourth embodiment, it is compared with the first embodiment. Thus, a semiconductor substrate having a nitride semiconductor thin film with a low dislocation density can be manufactured at a lower cost.

FIG. 1A to FIG. 1D are cross-sectional views showing a part of a semiconductor substrate manufacturing process (processes until heat treatment) according to a preferred embodiment of the present invention. 2A to 2E are cross-sectional views showing a part of the semiconductor substrate manufacturing process (process after heat treatment) according to a preferred embodiment of the present invention. It is a figure which shows an example of the cross-section of LED produced using the semiconductor substrate which concerns on this Embodiment. It is a figure which shows an example of the cross-sectional structure of the high frequency transistor produced using the semiconductor substrate which concerns on this Embodiment.

Explanation of symbols

1 Semiconductor substrate 2 Silicon substrate (second substrate)
3 GaN thin film (nitride semiconductor thin film)
11 GaN substrate (first nitride semiconductor substrate)
12 Ion implantation layer 13 Crack layer

Claims (11)

  A step of implanting ions in the vicinity of the surface of the first nitride semiconductor substrate, a step of superimposing the surface side of the first nitride semiconductor substrate on the second substrate, and heat-treating the two superimposed substrates And a step of peeling most of the first nitride semiconductor substrate from the second substrate with the ion-implanted layer as a boundary.   A step of implanting ions in the vicinity of the surface of the first nitride semiconductor substrate; a step of heat-treating the first nitride semiconductor substrate; and attaching the surface side of the first nitride semiconductor substrate to the second substrate. A method of manufacturing a semiconductor substrate, comprising: a step of combining, and a step of peeling most of the first nitride semiconductor substrate from the second substrate with an ion-implanted layer as a boundary.   3. The semiconductor substrate manufacturing method according to claim 1, wherein after the most part of the first nitride semiconductor substrate is peeled off, the ion-implanted layer is removed and reused as the first nitride semiconductor substrate. Method.   The method of manufacturing a semiconductor substrate according to claim 1, wherein the first nitride semiconductor substrate is made of wurtzite GaN or wurtzite AlN.   The method of manufacturing a semiconductor substrate according to claim 1, wherein a surface of the first nitride semiconductor substrate is a (000-1) nitrogen surface.   6. The surface according to claim 1, wherein the surface of the first nitride semiconductor substrate is a surface that is off-cut within a range of 0 ° or more and less than 8 ° in an arbitrary direction from the (000-1) nitrogen surface. A method for manufacturing a semiconductor substrate.   The method of manufacturing a semiconductor substrate according to claim 1, wherein the ions include one or more ions of hydrogen, nitrogen, oxygen, neon, and argon.   The method for manufacturing a semiconductor substrate according to claim 1, wherein the second substrate is made of any one of silicon, glass, and metal.   The method of manufacturing a semiconductor substrate according to claim 1, wherein the first nitride semiconductor substrate has a thickness of about 400 μm.   The method of manufacturing a semiconductor substrate according to claim 1, wherein the ion implantation is performed so as to have a concentration peak at a depth of 2 μm or less from the surface of the first nitride semiconductor substrate. The heat treatment is performed at a temperature of 800 ° C or higher for 2 hours or longer in a gas atmosphere composed of a single gas of hydrogen, nitrogen, ammonia, oxygen, argon, neon, or helium, or a mixed gas thereof. 10. A method for producing a semiconductor substrate according to claim 10.

Images