CN1716545A - Alxgayin1-x-yn substrate, cleaning method of alxgayin1-x-yn substrate, ain substrate, and cleaning method of AlN substrate - Google Patents

Alxgayin1-x-yn substrate, cleaning method of alxgayin1-x-yn substrate, ain substrate, and cleaning method of AlN substrate Download PDF

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CN1716545A
CN1716545A CN 200510082192 CN200510082192A CN1716545A CN 1716545 A CN1716545 A CN 1716545A CN 200510082192 CN200510082192 CN 200510082192 CN 200510082192 A CN200510082192 A CN 200510082192A CN 1716545 A CN1716545 A CN 1716545A
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substrate
peak area
acid
electronics
cleaning method
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CN100411111C (en
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上村智喜
石桥惠二
藤原伸介
中幡英章
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Sumitomo Electric Industries Ltd
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Abstract

An Al x Ga y In 1-x-y N substrate in which particles having a grain size of at least 0.2 m on a surface of the Al x Ga y In 1-x-y N substrate are at most 20 in number when a diameter of the Al x Ga y In 1-x-y N substrate is two inches, and a cleaning method with which the Al x Ga y In 1-x-y N substrate can be obtained are provided. Further, an Al x Ga y In 1-x-y N substrate (51) in which, in a photoelectron spectrum of a surface of the Al x Ga y In 1-x-y N substrate (51) by X-ray photoelectron spectroscopy with a detection angle of 10 DEG , a ratio between a peak area of C 1s electrons and a peak area of N 1s electrons (C 1s electron peak area / N 1s electron peak area) is at most 3, and a cleaning method with which the Al x Ga y In 1-x-y N substrate can be obtained are provided. Still further, an AlN substrate (52) in which, in a photoelectron spectrum of a surface of the AlN substrate (52) by X-ray photoelectron spectroscopy with a detection angle of 10 DEG , a ratio between a peak area of Al 2s electrons and a peak area of N 1s electrons (Al 2s electron peak area / N 1s electron peak area) is at most 0.65 and a cleaning method with which the AlN substrate can be obtained are provided.

Description

Al xGa yIn 1-x-yN substrate and cleaning method thereof, AlN substrate and cleaning method thereof
Technical field
The present invention relates to a kind of Al xGa yIn 1-x-yN (0＜x≤1,0＜y≤1, x+y≤1) substrate and this Al xGa yIn 1-x-yThe cleaning method of N (0＜x≤1,0＜y≤1, x+y≤1) substrate.The invention still further relates to a kind of AlN substrate of epitaxial film of the low turbidity water flat (haze level) of can stably growing, and the cleaning method of this AlN substrate.In this specification, Al xGa yIn 1-x-yN (0＜x≤1,0＜y≤1, x+y≤1) is abbreviated as Al xGa yIn 1-x-yN.
Background technology
Al xGa yIn 1-x-yThe N substrate can be used as the substrate of various semiconductor device, for example substrate of optics and/or electronic device suitably.
A kind of Al xGa yIn 1-x-yThe representative growing method of N crystal is HVPE (hydride vapour phase oriented growth) method, and from Al xGa yIn 1-x-yThe N crystal can be made Al xGa yIn 1-x-yThe N substrate.By at Al xGa yIn 1-x-yThe various epitaxial films of growth can obtain semiconductor device, for example optics and/or electronic device on the N substrate surface.
Al xGa yIn 1-x-yIn the N substrate, the band gap of AlN substrate is 6.2eV, and thermal conductivity is about 3.3WK -1Cm -1, and have high resistance, therefore used as the substrate of various semiconductor device, for example the substrate of optics and/or electronic device has caused people's attention.
Can make the AlN substrate with the AlN crystal that grows out by HVPE method or sublimation method.By the various epitaxial films of growth on the AlN substrate surface, can obtain semiconductor device, for example optics and/or electronic device.
For example, people such as Toshio Nishida are at Appl.Phys.Lett., 2003,82 volumes disclosed a kind of light-emitting diode that obtains by growth AlGaN film on the AlN substrate etc. in the 1st phase " GaN-free transparent ultraviolet light-emitting diodes ".In addition, people's such as Toshio Nishida " The Characteristics of UV-LED Grown on Bulk AlN Substrate UnderLarge Current Injection ", the 51st spring session of the Japan Society of Applied Physics and RelatedSocieties, the expansion summary, in March, 2004,409 pages, a kind of light-emitting diode that forms on bulk (bulk) AlN substrate is also disclosed.
Summary of the invention
Summary of the invention
When at Al xGa yIn 1-x-yDuring the growing epitaxial film, what grow sometimes is the low quality epitaxial film that a large amount of defectives and/or tarnishing (tarnishes) are arranged on the N substrate surface.Use the device property of semiconductor device of this low quality epitaxial film poor, so, need stably grow the high-quality epitaxial film of defectiveness seldom and/or tarnishing.
Therefore, for the high-quality epitaxial film of stably grow defectiveness seldom and/or tarnishing, attached to Al xGa yIn 1-x-yParticle and/or organic substance on the N substrate surface are removed by cleaning.But, owing to do not relate to Al xGa yIn 1-x-yParticle and/or organic substance are removed the routine techniques reference of degree on the N substrate surface, and its standard is also unclear, has Al xGa yIn 1-x-yThe variation of N substrate surface condition directly causes the problem of the mass change of epitaxial film.
In addition, when growing epitaxial film on the AlN substrate surface, grow the flat epitaxial film of ultra sometimes.Use the device property of semiconductor device of this epitaxial film poor, so, need stably grow the flat epitaxial film of low turbidity water.
Therefore, for the flat epitaxial film of the low turbidity water of stably growing, the AlN substrate is to be cleaned.But,, have Al because the standard of the AlN substrate surface of can the stable growth low turbidity water flat epitaxial film is unclear xGa yIn 1-x-yThe variation of N substrate surface condition directly causes the problem of epitaxial film mass change.
An object of the present invention is to provide a kind of Al of the epitaxial film of growing high-quality stably xGa yIn 1-x-yThe N substrate, and obtain this Al xGa yIn 1-x-yThe cleaning method of N substrate.Another object of the present invention provides a kind of AlN substrate of the flat epitaxial film of low turbidity water of can stably growing, and the cleaning method of this AlN substrate.
The present invention relates to a kind of Al xGa yIn 1-x-yThe N substrate is wherein worked as Al xGa yIn 1-x-yWhen the diameter of N substrate is 2 inches, Al xGa yIn 1-x-yThe population that grain size is at least 0.2 μ m on surface of N substrate is at most 20.Herein, in this manual, Al xGa yIn 1-x-yThe N substrate refers to the element nitride crystal substrate that comprises aluminium (Al), and it can also comprise gallium (Ga) and/or indium (In) except aluminium and nitrogen.
In addition, the present invention relates to a kind of Al xGa yIn 1-x-yThe cleaning method of N substrate is wherein with Al xGa yIn 1-x-yThe N substrate is immersed in a kind of cleaning solution of being made by the solution that is selected from ammoniacal liquor, ammonium hydroxide (ammonia hydroxide)/hydrogen peroxide mixture and the organic base aqueous solution, carry out simultaneously ultrasonic, thereby as this Al xGa yIn 1-x-yWhen the diameter of N substrate is two inches, make Al xGa yIn 1-x-yThe population that grain size is at least 0.2 μ m on surface of N substrate is at most 20.
Herein, at Al of the present invention xGa yIn 1-x-yIn the cleaning method of N substrate, the preferred ammoniacal liquor that uses ammonia concentration to be at least 0.5 percentage by weight, hydrogenperoxide steam generator concentration is at least the ammonium hydroxide/hydrogen peroxide mixture that 0.1 percentage by weight and ammonia concentration are at least 0.1 percentage by weight, and organic base concentration is at least the organic base aqueous solution of 0.5 percentage by weight as cleaning solution.
At Al of the present invention xGa yIn 1-x-yIn the N substrate cleaning method, preferred organic aqueous alkali is the organic base that is dissolved in the water, and this organic base is in tetramethylammonium hydroxide and the hydroxide 2-ethoxy trimethylammonium.
In addition, at Al of the present invention xGa yIn 1-x-yIn the N substrate cleaning method, Al xGa yIn 1-x-yThe soak time of N substrate was at least 30 seconds.
In addition, the present invention relates to a kind of Al xGa yIn 1-x-yThe N substrate is wherein detecting the Al that the angle obtains by the X-ray photoelectron spectroscopy method with 10 ° xGa yIn 1-x-yIn the N substrate surface photoelectron spectroscopy, C 1sThe peak area of electronics and N 1sRatio (C between the peak area of electronics 1sElectronics peak area/N 1sThe electronics peak area) is at most 3.
In addition, the present invention relates to a kind of Al xGa yIn 1-x-yThe cleaning method of N substrate is wherein with Al xGa yIn 1-x-yThe N substrate is immersed in the acid solution, detects the Al that the angle obtains thereby make by the X-ray photoelectron spectroscopy method with 10 ° xGa yIn 1-x-yIn the N substrate surface photoelectron spectroscopy, C 1sThe peak area of electronics and N 1sRatio (C between the peak area of electronics 1sElectronics peak area/N 1sThe electronics peak area) is at most 3.
Herein, at Al of the present invention xGa yIn 1-x-yIn the cleaning method of N substrate, preferred acid solution is the solution of being made by at least a acid that is selected from hydrofluoric acid, hydrochloric acid and the sulfuric acid, or the solution of being made by the mixture that is selected from least a acid in hydrofluoric acid, hydrochloric acid and the sulfuric acid and hydrogenperoxide steam generator.
In addition, at Al of the present invention xGa yIn 1-x-yIn the cleaning method of N substrate, when acid solution is the solution of being made by at least a acid that is selected from hydrofluoric acid, hydrochloric acid and the sulfuric acid, the total concentration of hydrofluoric acid, hydrochloric acid and sulfuric acid is at least 0.5 percentage by weight in the preferred acid solution, and when acid solution is the solution of being made by the mixture that is selected from least a acid in hydrofluoric acid, hydrochloric acid and the sulfuric acid and hydrogenperoxide steam generator, the total concentration of hydrofluoric acid, hydrochloric acid and sulfuric acid is at least 0.1 percentage by weight in the preferred acid solution, and the concentration of hydrogenperoxide steam generator is at least 0.1 percentage by weight simultaneously.
In addition, at Al of the present invention xGa yIn 1-x-yIn the N substrate cleaning method, preferred Al xGa yIn 1-x-yThe soak time of N substrate was at least 30 seconds.
The present invention relates to a kind of AlN substrate, wherein detecting in the AlN substrate surface photoelectron spectroscopy of angle acquisition Al with 10 ° by the X-ray photoelectron spectroscopy method 2sThe peak area of electronics and N 1sRatio (Al between the peak area of electronics 2sElectronics peak area/N 1sThe electronics peak area) is at most 0.65.
In addition, the present invention relates to a kind of cleaning method of AlN substrate, wherein the AlN substrate is immersed in the acid solution, thereby make by in the AlN substrate surface photoelectron spectroscopy of X-ray photoelectron spectroscopy method with 10 ° of detection angles acquisitions Al 2sElectronics peak area and N 1sRatio (Al between the electronics peak area 2sElectronics peak area/N 1sThe electronics peak area) is at most 0.65.
Herein, in AlN substrate cleaning method of the present invention, preferred acid solution is the acid solution of being made by at least a acid that is selected from nitric acid, phosphoric acid and acetic acid.
In addition, in AlN substrate cleaning method of the present invention, the concentration of preferred acid solution is at least 0.5 percentage by weight.
In addition, in AlN substrate cleaning method of the present invention, the soak time of preferred AlN substrate was at least 40 seconds.
According to the present invention, can provide a kind of Al of the epitaxial film of growing high-quality stably xGa yIn 1-x-yN substrate and this Al of acquisition xGa yIn 1-x-yThe cleaning method of N substrate.
In addition, can provide a kind of AlN substrate of the flat epitaxial film of low turbidity water of can growing and the cleaning method of this AlN substrate of acquisition.
Above-mentioned and other purposes of the present invention, feature, aspect and advantage will be described in detail and become clearer along with following the present invention who carries out in conjunction with the accompanying drawings.
Description of drawings
Fig. 1 and 2 is that diagram the present invention detects the schematic diagram of an example that the angle is 10 ° an x-ray photoelectron power spectrum.
Fig. 3 is the cleaning instrument schematic sectional view of using among the embodiment 1.
Fig. 4 has shown population in the epitaxial film of growing among the embodiment 1 and the relation between the number of defects on the AlN substrate surface.
Fig. 5 is the cleaning instrument schematic sectional view of using among the embodiment 2.
Fig. 6 is the cleaning instrument schematic sectional view of using among the embodiment 3.
Fig. 7 has shown among the embodiment 3 and to have cleaned Al on the AlN substrate later 2sElectronics peak area and N 1sRatio (Al between the electronics peak area 2sElectronics peak area/N 1sThe electronics peak area) and be grown in the relation of the turbidity level of the epitaxial film on this AlN substrate surface.
Preferred embodiment is described
The present invention relates to a kind of AlxGa yIn 1-x-yThe N substrate is wherein worked as AlxGa yIn 1-x-yWhen the diameter of N substrate is 2 inches, AlxGa yIn 1-x-yThe population that grain size is at least 0.2 μ m on surface of N substrate is at most 20. This is based on the inventor's following discovery: work as AlxGa yIn 1-x-yWhen the particle that grain size is at least 0.2 μ m on the N substrate surface is controlled within the above-mentioned quantity, can grow seldom defective high-quality epitaxial film.
Herein, AlxGa yIn 1-x-yPopulation on the N substrate surface is calculated with the following method: to AlxGa yIn 1-x-yAll particles that grain size is at least 0.2 μ m on the N substrate surface are counted, and the population that then number is gone out changes into hypothesis AlxGa yIn 1-x-yNumerical value when the N substrate diameter is 2 inches. Therefore, among the present invention, to AlxGa yIn 1-x-yThe size of N substrate without limits. For example, diameter is 4 inches AlxGa yIn 1-x-yThe area of N substrate is that diameter is 2 inches AlxGa yIn 1-x-yFour times of N Substrate Area. Therefore, be 4 inches Al when using diameterxGa yIn 1-x-yDuring the N substrate, 1/4 of its upper total number of particles in surface is equivalent to population used herein. Should be pointed out that particle counting is to carry out with the substrate surface inspection apparatus of well-known light scattering scheme etc. In addition, the material of particle there is not particular restriction.
The present invention relates to a kind of cleaning method, wherein with AlxGa yIn 1-x-yThe N substrate is immersed in the cleaning solution that is selected from ammoniacal liquor, ammonium hydroxide/hydrogen peroxide mixture and the organic base aqueous solution, carry out simultaneously ultrasonic, thereby as this AlxGa yIn 1-x-yWhen the diameter of N substrate is two inches, make AlxGa yIn 1-x-yThe population that grain size is at least 0.2 μ m on surface of N substrate is at most 20.
Herein, the ammonium hydroxide/hydrogen peroxide mixture refers to the mixture of hydrogenperoxide steam generator and ammoniacal liquor. In addition, the organic base aqueous solution refers to the organic base that is dissolved in the water, and the hydroxide 2-ethoxy trimethylammonium of the tetramethylammonium hydroxide of structural formula (1) expression below preferred use the and structural formula (2) expression one of them as organic base:
Figure A20051008219200091
When using ammoniacal liquor as cleaning solution, preferred ammonia relative concentration is at least 0.5 percentage by weight in whole cleaning solution. When using the ammonium hydroxide/hydrogen peroxide mixture as cleaning solution, preferably for whole cleaning solution, the concentration of hydrogenperoxide steam generator is at least 0.1 percentage by weight, and the concentration of ammonia is at least 0.1 percentage by weight. When using organic base as cleaning solution, preferred organic base is at least 0.5 percentage by weight with respect to the concentration of whole cleaning solution. By being defined as above the concentration of cleaning solution, AlxGa yIn 1-x-yPopulation on the N substrate surface trends towards by more stably as above control.
Preferred AlxGa yIn 1-x-yThe soak time of N substrate in cleaning solution is at least 30 seconds. In this case, because AlxGa yIn 1-x-yThe N substrate fully is immersed in the cleaning solution AlxGa yIn 1-x-yPopulation on the N substrate surface trends towards by more stably as above control. Herein, AlxGa yIn 1-x-yThe soak time of N substrate is to begin to calculate from cleaning fluid is carried out ultrasonic time point.
In addition, the present invention relates to a kind of AlxGa yIn 1-x-yThe N substrate is wherein detecting the Al that the angle obtains by the X-ray photoelectron spectroscopy method with 10 °xGa yIn 1-x-yIn the N substrate surface photoelectron spectroscopy, C1sThe peak area of electronics and N1sRatio (C between the peak area of electronics1sElectronics peak area/N1sThe electronics peak area) is at most 3. This is based on the inventor's following discovery: work as C1sThe peak area of electronics and N1sWhen the ratio between the peak area of electronics is as above controlled, can grow high-quality epitaxial film without any tarnishing. Detect the Al that the angle obtains by X-ray photoelectron spectroscopy (XPS) method with 10 ° herein,xGa yIn 1-x-yC in the N substrate surface photoelectron spectroscopy1sThe peak area of electronics and N1sRatio between the peak area of electronics has indicated AlxGa yIn 1-x-yOrganic matter is with respect near Al on the N substrate surfacexGa yIn 1-x-yThe quantity of the nitrogen of N substrate surface. By its ratio is as above controlled, can grow the high-quality epitaxial film without any tarnishing.
Herein, C1sElectronics refers to the electronics on C (carbon) the 1s track, and N1sElectronics refers to the electronics on N (nitrogen) the 1s track. As shown in Figure 1, by the irradiation of X ray 61, AlxGa yIn 1-x-yN substrate 51 lip-deep C1sElectronics and N1sElectronics is released with photoelectron 71 forms. After this, with and AlxGa yIn 1-x-yThe photoelectron 71 monitored devices 81 that N substrate 51 surfaces become 10 ° direction to discharge detect (detecting 10 ° at angle), thereby obtain photoelectron spectroscopy. Determine the C of this photoelectron spectroscopy1sThe peak area of electronics and N1sRatio between the peak area of electronics.
In addition, the present invention relates to a kind of cleaning method, wherein with AlxGa yIn 1-x-yThe N substrate is immersed in a kind of acid solution, detects the Al that the angle obtains thereby make by the X-ray photoelectron spectroscopy method with 10 °xGa yIn 1-x-yIn the N substrate surface photoelectron spectroscopy, C1sThe peak area of electronics and N1sRatio (C between the peak area of electronics1sElectronics peak area/N1sThe electronics peak area) is at most 3.
Herein, preferred acid solution is the solution that is selected from least a acid in hydrofluoric acid, hydrochloric acid and the sulfuric acid. More preferably acid solution is to be selected from least a acid in hydrofluoric acid, hydrochloric acid and the sulfuric acid and the mixture of hydrogenperoxide steam generator. In this case, as above C in the photoelectron spectroscopy1sThe peak area of electronics and N1sRatio between the peak area of electronics is tended to more stably be controlled at be at most 3.
In addition, when acid solution was the solution of being made by at least a acid that is selected from hydrofluoric acid, hydrochloric acid and the sulfuric acid, the total concentration of hydrofluoric acid, hydrochloric acid and sulfuric acid was at least 0.5 percentage by weight in the preferred acid solution. In addition, when acid solution is the solution of being made by the mixture of at least a acid that is selected from hydrofluoric acid, hydrochloric acid and sulfuric acid and hydrogenperoxide steam generator, the total concentration of hydrofluoric acid, hydrochloric acid and sulfuric acid is at least 0.1 percentage by weight in the preferred acid solution, and the concentration of hydrogenperoxide steam generator is at least 0.1 percentage by weight simultaneously. In this case, as above C in the photoelectron spectroscopy1sThe peak area of electronics and N1sRatio between the peak area of electronics is tended to more stably be controlled at be at most 3.
Preferred Al alsoxGa yIn 1-x-yThe soak time of N substrate in acid solution is at least 30 seconds. In this case, because AlxGa yIn 1-x-yThe N substrate fully is immersed in the acid solution, as above C1sThe peak area of electronics and N1sRatio between the peak area of electronics is tended to by more stably as above control.
In addition, the present invention relates to a kind of AlN substrate, wherein detecting in the AlN substrate surface photoelectron spectroscopy of angle acquisition Al with 10 ° by X-ray photoelectron spectroscopy (XPS) method2sThe peak area of electronics and N1sRatio (Al between the peak area of electronics2sElectronics peak area/N1sThe electronics peak area) is at most 0.65. This is based on the inventor's following discovery: work as Al2sElectronics peak area and N1sWhen the ratio between the electronics peak area is as above controlled, can grow the flat epitaxial film of low turbidity water.
When using MOVPE method (metal-organic chemical vapour deposition growth method) or MBE method (molecular beam epitaxy) at AlN substrate growing epitaxial film, the surface of heating AlN substrate before growing film. Because by heating AlN substrate surface, the volatile quantity of AlN substrate surface N (nitrogen) surpasses Al (aluminium), when the growing epitaxial film, comprises a large amount of Al in the chemical composition of AlN substrate surface. Therefore, in its chemical composition, comprise in advance a large amount of N by making the AlN substrate surface, can grow the flat epitaxial film of low turbidity water. This is based on the inventor's following discovery: can use a kind of like this AlN substrate, and in the photoelectron spectroscopy of this AlN substrate surface that detects the angle acquisition by X-ray photoelectron spectroscopy (XPS) method with 10 °, Al2sThe peak area of electronics and N1sRatio between the peak area of electronics is at most 0.65, as the standard of AlN substrate surface.
Herein, Al2sElectronics refers to the electronics on Al (aluminium) the 2s track, and N1sElectronics refers to the electronics on the 1s track of N. As shown in Figure 2, by the irradiation of X ray 62, AlN substrate 52 lip-deep Al2sElectronics and N1sElectronics is released with photoelectron 72 forms. After this, detecting (detecting 10 ° at angle) with photoelectron 72 monitored devices 82 that AlN substrate 52 surface becomes 10 ° direction to discharge, thus the acquisition photoelectron spectroscopy. Determine the Al of this photoelectron spectroscopy2sThe peak area of electronics and N1sRatio between the peak area of electronics.
In addition, the present invention relates to a kind of cleaning method, wherein the AlN substrate is immersed in the acid solution, thereby make by in the AlN substrate surface photoelectron spectroscopy of X-ray photoelectron spectroscopy method with 10 ° of detection angles acquisitions Al2sThe peak area of electronics and N1sRatio (Al between the peak area of electronics2sElectronics peak area/N1sThe electronics peak area) is at most 0.65.
Herein, preferred acid solution is the solution of being made by at least a acid that is selected from hydrofluoric acid, hydrochloric acid and the sulfuric acid, or by at least two kinds of mixed solutions of making in these acid. In this case, as above Al2sThe peak area of electronics and N1sRatio between the peak area of electronics is tended to more stably be controlled at be at most 0.65.
In addition, the relative concentration of preferred acid solution is at least 0.5 percentage by weight in whole acid solution. In this case, as above Al in the photoelectron spectroscopy2sThe peak area of electronics and N1sRatio between the peak area of electronics is tended to more stably be controlled at be at most 0.65.
The preferred soak time of AlN substrate in acid solution is at least 40 seconds. In this case, because the AlN substrate fully is immersed in the acid solution Al2sThe area at electronics peak and N1sRatio between the peak area of electronics is tended to more stably as above be controlled at be at most 0.65.
Embodiment
Embodiment
Embodiment 1
At first, prepare 50 diameters and be 2 inches AlN substrate, each substrate all is that the AlN crystal by the growth of HVPE method is carried out mirror ultrafinish, and damaged layer obtains owing to mirror ultrafinish is removed then.Herein, the thickness of 50 each sheets of AlN substrate all is 400 μ m, and the AlN substrate surface is the plane of (0001) 2 ° of offset alignment.
Then, use the cleaning instrument shown in Fig. 3 schematic sectional view, 50 AlN substrates are cleaned with different separately soak times.Herein, the cleaner bath shown in Fig. 3 13 is full of the tetramethylammonium hydroxide aqueous solution of various concentration as cleaning solution 23.With frequency is the cleaning fluid 23 that the ultrasonic wave 33 of 900kHz has been applied to soak AlN substrate 43, and each all is identical to ultrasound condition for 50 AlN substrates 43.
Then, for the AlN substrate after each cleaning, the particle that grain size on the AlN substrate surface is at least 0.2 μ m is counted with the substrate surface inspection apparatus of light scattering scheme.
After this, under the same conditions, on each substrate surface of 50 AlN substrates, grow the thick epitaxial film that forms by the AlN crystal of 1 μ m by MOVPE method (metal-organic chemical vapour deposition growth method).Then, use the substrate surface inspection apparatus identical that the number of defects of epitaxial film is counted with above-mentioned instrument.
Fig. 4 has shown this result of experiment.Among Fig. 4, abscissa represents to be at least with grain size on the AlN substrate surface after the cleaning of aforesaid way counting the population of 0.2 μ m, and the number of defects of the epitaxial film of growing on the AlN substrate surface that ordinate is represented is corresponding with the abscissa population, number goes out.
As shown in Figure 4, when diameter is grain size is at least 0.2 μ m on 2 inches the AlN substrate surface a population when being at most 20, number of defects is less than 50 in the epitaxial film of growing on this surface.Therefore, 20 the situation of surpassing with population is compared, acquisition be the less high-quality epitaxial film of defective.
The population that grain size is at least 0.2 μ m on the surface is at most 20 AlN substrate and cleans with cleaning solution, the concentration of tetramethylammonium hydroxide is at least 0.5 percentage by weight in the cleaning solution for whole cleaning solution, and soak time was at least 30 seconds.
Although what use in the foregoing description 1 is the AlN substrate, thinks and use the Al that is different from the AlN substrate xGa yIn 1-x-yThe N substrate also can obtain similar result.In addition, as mentioned above, to the thickness of AlN substrate and planar orientation without limits, they can obtain to be similar to the result of embodiment 1 during for any number.
Embodiment 2
At first, be similar to embodiment 1, prepare 50 diameters and be 2 inches AlN substrate, each substrate all is that the AlN crystal is carried out mirror ultrafinish, and damaged layer obtains owing to mirror ultrafinish is removed then.Herein, the thickness of 50 each sheets of AlN substrate all is 400 μ m, and the AlN substrate surface is the plane of (0001) 2 ° of offset alignment.
Then, use the cleaning instrument shown in Fig. 5 schematic sectional view, 50 AlN substrates are cleaned with different separately soak times.Herein, the cleaner bath 15 shown in Fig. 5 is full of the hydrochloric acid of various concentration as acid solution 25, to soak each AlN substrate 45.
Then, for each AlN substrate that cleaned, use x-ray photoelectron spectroscopy, the K alpha ray that adopts Mg with 10 ° of photoelectron spectroscopies that detect angular measurement AlN substrate surface, calculates C as x-ray source 1sThe peak area of electronics and N 1sRatio (C between the peak area of electronics 1sElectronics peak area/N 1sThe electronics peak area).
After this, under the same conditions, on each substrate surface of 50 AlN substrates, grow the thick epitaxial film that forms by the AlN crystal of 1 μ m by the MOVPE method.Then, for each epitaxial film that grows by this way, whether exist based on following standard visually rank tarnishing.For each class (C as shown in table 1 1sElectronics peak area/N 1sThe electronics peak area), number is provided the epitaxial film quantity of tarnishing, the results are shown in Table 1.
Table 1
(C 1sElectronics peak area/N 1sThe electronics peak area) Be at most 3 Greater than 3 and be at most 5 Greater than 5
AlN substrate number/AlN substrate sum with tarnishing 0/15 5/27 7/8
The evaluation criteria that tarnishing exists
Tarnishing exists---and it is a minute surface that the part of epitaxial film is not polished
Tarnishing does not exist---and it is a minute surface that epitaxial film all is polished
As table 1 as seen, there is C 1sThe peak area of electronics and N 1sRatio (C between the peak area of electronics 1sElectronics peak area/N 1sThe electronics peak area) the few more trend of more little tarnishing.Particularly when this ratio is at most 3, do not have tarnishing on the epitaxial film, what grow is the high-quality epitaxial film.
C 1sThe peak area of electronics and N 1sRatio (C between the peak area of electronics 1sElectronics peak area/N 1sThe electronics peak area) be at most 3 AlN substrate and clean with cleaning solution, the concentration of hydrochloric acid is at least 0.5 percentage by weight in the described cleaning solution for whole cleaning solution, and soak time was at least 30 seconds.
Although what use in the foregoing description 2 is the AlN substrate, thinks and use the Al that is different from the AlN substrate xGa yIn 1-x-yThe N substrate also can obtain similar result.In addition, as mentioned above, to the thickness of AlN substrate and planar orientation without limits, they can obtain to be similar to the result of embodiment 2 during for any number.
Embodiment 3
At first, prepare 50 diameters and be 2 inches AlN substrate, each substrate all is that the AlN crystal by the growth of HVPE method is carried out mirror ultrafinish, and damaged layer obtains owing to mirror ultrafinish is removed then.Herein, the thickness of 50 each sheets of AlN substrate all is 400 μ m, and the AlN substrate surface is the plane of (0001) 2 ° of offset alignment.
Then, use the cleaning instrument shown in Fig. 6 schematic sectional view, each all cleans to 50 AlN substrates.Herein, the cleaner bath 16 shown in Fig. 6 is full of nitric acid, phosphoric acid and the acetic acid mixed solution of various concentration as cleaning solution 26, cleans AlN substrate 46 with different scavenging periods.
Then, for each AlN substrate that cleaned, use x-ray photoelectron spectroscopy, the K alpha ray that adopts Mg with 10 ° of photoelectron spectroscopies that detect angular measurement AlN substrate surface, calculates Al as x-ray source 2sThe peak area of electronics and N 1sRatio (Al between the peak area of electronics 2sElectronics peak area/N 1sThe electronics peak area).
After this, under the same conditions, on each substrate surface of 50 AlN substrates, grow the thick epitaxial film that forms by the AlN crystal of 1 μ m by the MOVPE method.Then, with the substrate surface inspection apparatus of light scattering scheme, each epitaxial film that grows is by this way carried out the turbidity level assessment.The results are shown in Figure 7.Among Fig. 7, the Al of that abscissa is represented to obtain with x-ray photoelectron spectroscopy, the AlN substrate after cleaning 2sThe peak area of electronics and N 1sRatio (Al between the peak area of electronics 2sElectronics peak area/N 1sThe electronics peak area), and ordinate be illustrated in and have (Al shown in the abscissa 2sElectronics peak area/N 1sThe electronics peak area) turbidity level of the epitaxial film that grows on each AlN substrate of numerical value.
As shown in Figure 7, there is Al 2sThe peak area of electronics and N 1sRatio (Al between the peak area of electronics 2sElectronics peak area/N 1sThe electronics peak area) the low more trend of the turbidity level of more little epitaxial film.Particularly when this ratio was at most 0.65, the turbidity level of epitaxial film was lower than 2ppm, and the epitaxial film that grows is fabulous.
Al 2sElectronics peak area and N 1sRatio (Al between the electronics peak area 2sElectronics peak area/N 1sThe electronics peak area) be at most 0.65 AlN substrate and clean with acid solution, the concentration of nitric acid, phosphoric acid and acetic acid is at least 0.5 percentage by weight in the described acid solution for whole cleaning solution, and soak time was at least 40 seconds.
Although what use in the foregoing description 3 is the mixed solution of nitric acid, phosphoric acid and acetic acid, think a kind of acid in use nitric acid, phosphoric acid and the acetic acid perhaps also can obtain similar result by two kinds of mixed solutions of making in these acid.
In addition, as mentioned above, to the thickness of AlN substrate and planar orientation without limits, they can obtain to be similar to the result of embodiment 3 during for any number.
The present invention goes for making use Al xGa yIn 1-x-yThe semiconductor device of N substrate.In addition, the present invention also is applicable to and makes the semiconductor device that uses the AlN substrate.
Although the present invention is described in detail and illustrates, recognize with should be understood that above-mentioned illustrate with embodiment only be explanation and for example, implication without limits, aim of the present invention and scope are limited by the appended claim clause only.

Claims (15)

1, a kind of Al xGa yIn 1-x-yThe N substrate, wherein
As described Al xGa yIn 1-x-yWhen the diameter of N substrate is 2 inches, described Al xGa yIn 1-x-yThe population that grain size is at least 0.2 μ m on surface of N substrate is at most 20.
2, a kind of Al xGa yIn 1-x-yThe cleaning method of N substrate (43), wherein
With described Al xGa yIn 1-x-yN substrate (43) is immersed in a kind of cleaning solution of being made by the solution that is selected from ammoniacal liquor, ammonium hydroxide/hydrogen peroxide mixture and the organic base aqueous solution, carries out ultrasonic (33) simultaneously, thereby as this Al xGa yIn 1-x-yWhen the diameter of N substrate (43) is two inches, make Al xGa yIn 1-x-yThe population that grain size is at least 0.2 μ m on (43) surfaces of N substrate is at most 20.
3, the Al of claim 2 xGa yIn 1-x-yThe cleaning method of N substrate (43), wherein
Use ammonia concentration to be at least the ammoniacal liquor of 0.5 percentage by weight, hydrogenperoxide steam generator concentration is at least the ammonium hydroxide/hydrogen peroxide mixture that 0.1 percentage by weight and ammonia concentration are at least 0.1 percentage by weight, and organic base concentration is at least the organic base aqueous solution of 0.5 percentage by weight as described cleaning solution (23).
4, the Al of claim 2 xGa yIn 1-x-yThe cleaning method of N substrate (43), wherein
The described organic base aqueous solution is the organic base that is dissolved in the water, and described organic base is in tetramethylammonium hydroxide and the hydroxide 2-ethoxy trimethylammonium.
5, the Al of claim 2 xGa yIn 1-x-yThe cleaning method of N substrate (43), wherein
Described Al xGa yIn 1-x-yThe soak time of N substrate (43) was at least 30 seconds.
6, a kind of Al xGa yIn 1-x-yN substrate (51), wherein
Detecting the described Al that the angle obtains by the X-ray photoelectron spectroscopy method with 10 ° xGa yIn 1-x-yIn the photoelectron spectroscopy on N substrate (51) surface, C 1sThe peak area of electronics and N 1sRatio (C between the peak area of electronics 1sElectronics peak area/N 1sThe electronics peak area) is at most 3.
7, a kind of Al xGa yIn 1-x-yThe cleaning method of N substrate (45), wherein
With described Al xGa yIn 1-x-yN substrate (45) is immersed in the acid solution (25), thereby is detecting the Al that the angle obtains by the X-ray photoelectron spectroscopy method with 10 ° xGa yIn 1-x-yIn N substrate (45) the surface light electron spectrum, make C 1sThe peak area of electronics and N 1sRatio (C between the peak area of electronics 1sElectronics peak area/N 1sThe electronics peak area) is at most 3.
8, the Al of claim 7 xGa yIn 1-x-yThe cleaning method of N substrate (45), wherein
Described acid solution (25) is to be made by at least a acid that is selected from hydrofluoric acid, hydrochloric acid and the sulfuric acid, or make by the mixture that is selected from least a acid in hydrofluoric acid, hydrochloric acid and the sulfuric acid and hydrogenperoxide steam generator.
9, the Al of claim 8 xGa yIn 1-x-yThe cleaning method of N substrate (45), wherein
When described acid solution (25) be by be selected from that at least a acid in hydrofluoric acid, hydrochloric acid and the sulfuric acid makes the time, the total concentration of hydrofluoric acid, hydrochloric acid and sulfuric acid is at least 0.5 percentage by weight in the described acid solution (25), and
When described acid solution (25) be by the mixture that is selected from least a acid in hydrofluoric acid, hydrochloric acid and the sulfuric acid and hydrogenperoxide steam generator make the time, the total concentration of hydrofluoric acid, hydrochloric acid and sulfuric acid is at least 0.1 percentage by weight in the acid solution (25), and the concentration of hydrogenperoxide steam generator is at least 0.1 percentage by weight simultaneously.
10, the Al of claim 7 xGa yIn 1-x-yThe cleaning method of N substrate (45), wherein
Described Al xGa yIn 1-x-yThe soak time of N substrate (45) was at least 30 seconds.
11, a kind of AlN substrate (52), wherein
In the photoelectron spectroscopy on AlN substrate (52) surface of detecting the angle acquisition by the X-ray photoelectron spectroscopy method with 10 °, Al 2sThe peak area of electronics and N 1sRatio (Al between the peak area of electronics 2sElectronics peak area/N 1sThe electronics peak area) is at most 0.65.
12, the cleaning method of a kind of AlN substrate (46), wherein
Described AlN substrate (46) is immersed in the acid solution (26), thereby in the photoelectron spectroscopy on AlN substrate (46) surface of detecting the angle acquisition by the X-ray photoelectron spectroscopy method with 10 °, makes Al 2sThe peak area of electronics and N 1sRatio (Al between the peak area of electronics 2sElectronics peak area/N 1sThe electronics peak area) is at most 0.65.
13, the cleaning method of the AlN substrate (46) of claim 12, wherein
Described acid solution (26) is to be made by at least a acid that is selected from nitric acid, phosphoric acid and the acetic acid.
14, the cleaning method of the AlN substrate (46) of claim 12, wherein
The concentration of described acid solution (26) is at least 0.5 percentage by weight.
15, the cleaning method of the AlN substrate (46) of claim 12, wherein
The soak time of described AlN substrate (46) was at least 40 seconds.
CNB2005100821926A 2004-07-01 2005-07-01 Alxgayin1-x-yn substrate, cleaning method of alxgayin1-x-yn substrate, ain substrate, and cleaning method of AlN substrate Expired - Fee Related CN100411111C (en)

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