WO2015181971A1 - バルク状炭化珪素単結晶の評価方法、及びその方法に用いられる参照用炭化珪素単結晶 - Google Patents
バルク状炭化珪素単結晶の評価方法、及びその方法に用いられる参照用炭化珪素単結晶 Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 255
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 242
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/24—Measuring force or stress, in general by measuring variations of optical properties of material when it is stressed, e.g. by photoelastic stress analysis using infrared, visible light, ultraviolet
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L5/00—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes
- G01L5/0047—Apparatus for, or methods of, measuring force, work, mechanical power, or torque, specially adapted for specific purposes measuring forces due to residual stresses
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
Definitions
- the present invention relates to a method for evaluating a bulk silicon carbide single crystal and a silicon carbide single crystal for reference used in the method. More specifically, Raman spectroscopy is used for a plurality of bulk silicon carbide single crystals to be evaluated.
- the present invention also relates to a bulk silicon carbide single crystal evaluation method capable of relatively evaluating the magnitude of lattice distortion, and a reference silicon carbide single crystal used in the method.
- Silicon carbide is a wide bandgap semiconductor with a wide forbidden band of 2.2 to 3.3 eV, and has been researched and developed as an environmentally resistant semiconductor material because of its excellent physical and chemical characteristics. ing. In particular, in recent years, it has been attracting attention as a material for power semiconductors, short-wavelength optical devices from blue to ultraviolet, high-frequency electronic devices, high-voltage / high-power electronic devices, and research on device (semiconductor element) fabrication using SiC. Development is fostering.
- SiC single crystal substrate is generally cut into a thin plate having a thickness of about 300 to 600 ⁇ m using a multi-wire saw or the like and subjected to various polishing processes. Is manufactured.
- the crystal growth is usually performed by forming a temperature gradient so that the seed crystal side has a lower temperature than the SiC crystal powder side that is the raw material of the growth crystal.
- the inside of the growth space is controlled so that a moderately convex isotherm is formed in the growth direction so that a high-quality SiC single crystal ingot can be obtained.
- these temperature differences in the growth space also cause thermal stress to remain in the SiC single crystal grown thereby. Since such thermal stress differs for each obtained ingot, for example, when cutting with a multi-wire saw, a crack may be generated in the ingot as an unexpected trouble.
- processing strain is usually removed by diamond polishing, chemical mechanical polishing (CMP), etc., but if it remains or if the SiC single crystal substrate has thermal stress as an internal stress, it is useful for device manufacturing applications.
- CMP chemical mechanical polishing
- the average over the entire layer of the stacked structure is determined using Raman spectroscopy.
- a method for evaluating the amount of lattice distortion of a GaN layer is disclosed (see Patent Document 3). In this method, the Raman shift is measured so that the excitation light reaches all the layers in the laminated structure, and converted to the a-axis lattice strain amount of the GaN layer based on a known value.
- Patent Document 3 for micro LSIs in which dissimilar metals are bonded on a Si substrate, the stress distribution around the titanium silicide pattern and the element isolation film in the micro LSI is measured using micro Raman spectroscopy. Although a measured example has been reported (see Non-Patent Document 1), it is said that a large stress of 150 to 350 MPa is applied to the Si substrate around the titanium silicide pattern, and a large lattice strain is also induced. It is a measurement in the state which was done.
- the Raman shift is easily affected by the fluctuation of the wavelength of the laser beam of the Raman spectrometer used for measurement and the thermal distortion of the measuring instrument, and the reproducibility of the measurement is not sufficient. Therefore, although the Raman shift can be measured in principle or research, it is not suitable for evaluating the lattice strain of a single crystal in industrial production applications.
- the present inventors conducted extensive studies on a method for evaluating the degree of lattice distortion in a bulk SiC single crystal such as a SiC single crystal ingot or a SiC single crystal substrate. And measuring each Raman shift of a plurality of bulk SiC single crystals to be evaluated, obtaining a difference from the Raman shift of the reference SiC single crystal, and comparing these differences relative to each other. By comparing, it discovered that the magnitude
- an object of the present invention is to provide a method capable of relatively evaluating the degree of lattice distortion of a plurality of bulk SiC single crystals to be evaluated.
- Another object of the present invention is to provide a reference SiC single crystal used in a method of relatively evaluating the degree of lattice distortion of a bulk SiC single crystal.
- the present invention measures the Raman shift R ref of a reference silicon carbide single crystal as a reference, and measures the Raman shift R n of each of a plurality of bulk silicon carbide single crystals to be evaluated.
- the difference between each Raman shift R n and the Raman shift R ref is obtained, and the difference is relatively compared, so that the magnitude of lattice distortion in a plurality of bulk silicon carbide single crystals to be evaluated is relatively evaluated.
- This is a method for evaluating a bulk silicon carbide single crystal.
- the present invention is a silicon carbide single crystal for reference used in the above method, having a size of 5 mm square to 50 mm square, a thickness of 100 ⁇ m to 2000 ⁇ m, and a surface roughness Ra of 1 nm. And used for evaluation of bulk silicon carbide single crystal, characterized in that the micropipe density is 1.0 piece / cm 2 or less and the dislocation density is 5 ⁇ 10 3 pieces / cm 2 or less. This is a silicon carbide single crystal for reference.
- the SiC single crystal has a strong covalent bond.
- the Raman shift due to internal stress is negligible. This is because the Young's modulus of SiC is around 479.3 to 521.6 GPa (The Single Crystal Elastic Elastic Constants of Hexagonal SiC to C 1000 to Nov 10.70, Z. Li Li & R. C. Bradt, IntJ High Tech Technology 4 1-10), which is also related to about 2 to 3 times that of Si, which is about 130 to 180 GPa.
- Fig. 1 shows the results of measuring the Raman shift (cm -1 ) once a day for the same sample using a bulk SiC single crystal piece with a thickness of about 350 ⁇ m. It can be seen that the value varies.
- the thermal stress during the growth of a SiC single crystal by the sublimation recrystallization method is generally estimated to be about 10 to 100 MPa, and the strain amount is estimated to be about 1 / 10,000 to 1 / 1,000,000.
- the effects of wavelength fluctuations and thermal distortion of the measuring instrument are considered to be comparable to or higher than these values. Therefore, even if the same sample is measured, the value changes in the order of 1 / 1,000 to 1 / 10,000, and sufficient measurement reproducibility cannot be obtained.
- the same reference SiC single crystal is used when relatively evaluating the bulk SiC single crystal. That is, with respect to the Raman shift R ref of the reference SiC single crystal, the difference between the Raman shift R n and the Raman shift R ref for each bulk SiC single crystal to be evaluated is obtained, thereby determining the bulk SiC to be evaluated. Since the lattice distortion in the single crystal is relatively evaluated, any reference SiC single crystal can be used as the reference SiC single crystal.
- the bulk SiC single crystal to be evaluated is preferably used. It is better to keep the crystal and polytype the same. More preferably, from the viewpoint of facilitating relative comparison by making the difference between the Raman shift R n and the Raman shift R ref larger, the reference SiC single crystal suppresses lattice distortion as much as possible. It should be a thing.
- the thickness of the reference SiC single crystal is preferably 2000 ⁇ m or less. At this time, there is no problem in measurement if the thickness is 1 ⁇ m or more in terms of the focal depth at the time of Raman shift measurement, but the handling of the SiC single crystal for reference including the viewpoint of handling properties such as prevention of cracking is possible.
- the thickness is preferably 100 ⁇ m or more and 2000 ⁇ m or less.
- the measurement of Raman shift itself is sufficient if it has a size of about 5 mm ⁇ 5 mm (5 mm square), but considering the handling properties, the size of the reference SiC single crystal is 5 mm square or more and 50 mm square or less, preferably 10 mm. It is preferable that the angle is not less than 50 mm square.
- compressive stress tends to exist in the center of the cross section, and conversely, tensile stress tends to exist in the peripheral edge (edge).
- the reference SiC single crystal should be of high quality with few dislocations and defects from the viewpoint of preventing disturbances in Raman shift measurement.
- the micropipe density is 1 / cm 2 or less (more preferably 0 / cm 2 ), and the dislocation density is 5000 / cm 2 or less.
- 4H single polytype SiC single crystal is preferable, and the nitrogen concentration is preferably 5 ⁇ 10 18 to 5 ⁇ 10 19 atoms / cm 3 . When the nitrogen concentration is lower than this range, polytypes such as 6H other than 4H are likely to be generated. Conversely, when the nitrogen concentration is higher than this range, 3C type or stacking faults are likely to occur.
- the processing strain in producing the reference SiC single crystal is removed by diamond polishing, chemical mechanical polishing (CMP) or the like.
- CMP chemical mechanical polishing
- both the Si surface and the C surface should have the same level of surface roughness.
- the surface roughness Ra is 1 nm or less, preferably the surface roughness Ra is 0.2 nm or less.
- the SiC single crystal for reference is removed from the influence of the strain caused by the strain difference between the front and back surfaces.
- the surface of both the Si and C faces of the reference SiC single crystal should be treated by chemical mechanical polishing, thereby ensuring the intensity of Raman scattering without attenuating scattered light. Can do.
- the surface roughness Ra represents the arithmetic average roughness specified in JIS B0601 (1994).
- the reference SiC single crystal is placed in a plastic tray, the handling becomes easy and contamination by sebum in the hands can be prevented.
- the reference SiC single crystal has as good a crystallinity as possible and the crystal lattice having high completeness can be used to ensure the quantitativeness of the evaluation method according to the present invention.
- an evaluation method called an X-ray rocking curve can be used. X-ray rocking curves are obtained by making monochromatic X-rays with good parallelism incident on a single crystal substrate or the like, and comparing measured diffraction intensity curves with theoretically calculated diffraction intensity curves. This is a method for evaluating strain.
- the straightness of the plane of the C plane is measured from the angle analysis of diffraction lines by X-ray projection onto the C plane, and the integrity of the crystal is evaluated.
- the reference SiC single crystal has a 4H type polytype, and It is preferable to use one having the following lattice constant ⁇ range 1>, more preferably one having the following lattice constant ⁇ range 2>.
- the lattice constant slightly changes depending on the concentration of a doping element such as N. If it is such a lattice constant, It is thought that it is a SiC single crystal of almost typical natural appearance.
- the bulk SiC single crystal to be evaluated for example, a SiC single crystal ingot produced by a sublimation recrystallization method, a thin plate-like SiC single crystal cut from a SiC single crystal ingot, and a SiC single crystal after various polishings.
- the evaluation method of the present invention can be suitably used when the lattice distortion of the bulk SiC single crystal is expected to have some influence upon processing.
- the SiC single crystal ingot in order to predict the occurrence of cracks or the like in wire processing for slicing a SiC single crystal ingot into a thin plate shape or in side processing of an ingot in which a SiC single crystal ingot is peripherally ground into a cylindrical shape,
- the SiC single crystal ingot can be evaluated by this method.
- the SiC single crystal substrate when an epitaxial film is grown on a SiC single crystal substrate, the SiC single crystal substrate can be evaluated by the method of the present invention in order to predict the occurrence of warpage or the like.
- the lower limit of the thickness of the bulk SiC single crystal is not particularly limited, but when considering the penetration depth of the laser beam and the attenuation of scattered light, it is preferable to target the SiC single crystal having a thickness of 10 ⁇ m or more.
- the method of the present invention is suitable for evaluating lattice distortion of a single bulk SiC single crystal, but does not exclude use for evaluation in a state where other members or crystals are laminated. Absent.
- the focal depth of the incident laser beam when measuring the Raman shift, by setting the focal depth of the incident laser beam to a depth of about 1 to 100 ⁇ m, the internal stress of the bulk SiC single crystal, such as the thermal stress caused by the thermal gradient in sublimation recrystallization.
- the lattice distortion due to can be evaluated.
- the focal depth is shallower than this, the lattice distortion due to processing distortion such as slicing is evaluated, and the focal depth of the incident laser beam may be appropriately selected as necessary.
- the bulk SiC single crystal to be evaluated has a thickness of 500 ⁇ m or less, the bulk SiC single crystal is attached to a support pedestal having a horizontal mounting surface, and the Raman shift is measured to warp.
- the location where the Raman shift is measured is, for example, the center of the SiC single crystal substrate, the edge of the periphery, or the surface of the growth surface or the seed crystal side if the SiC single crystal ingot is used.
- a common location may be selected according to the purpose.
- the evaluation method of the present invention measures the Raman shift R n at least one point to be evaluated of the bulk SiC single crystal, and obtains a difference between Raman shift R ref of the reference SiC single crystal, relatively comparing the difference
- the magnitude of lattice distortion in a plurality of bulk SiC single crystals to be evaluated is relatively evaluated. That is, it is not necessary to measure the strain between all the lattices of the bulk SiC single crystal to be evaluated, and based on the strain of the lattice at the focal depth of the incident laser beam at the measurement location, It is determined whether or not the SiC single crystal contains more strain than other types.
- the conditions such as wire processing are made relatively gentle, or annealing (annealing) is performed in advance.
- Generation of cracks can be prevented beforehand by performing a process of removing stress.
- a bulk SiC single crystal that has been annealed may be evaluated again by the method of the present invention.
- the degree of lattice distortion can be relatively evaluated for a plurality of bulk SiC single crystals to be evaluated. Therefore, for example, it is possible to prevent the occurrence of cracks when processing a SiC single crystal ingot, or to prevent the occurrence of warpage when growing an epitaxial film on a SiC single crystal substrate.
- FIG. 1 shows the result of measuring the Raman shift of a SiC single crystal piece by changing the measurement date.
- FIG. 2 is a schematic explanatory view showing a state in which the reference SiC single crystal is taken out from the SiC single crystal ingot.
- 3A shows the X-ray rocking curve of the reference SiC single crystal used in Example 1
- FIG. 3B shows the X-ray rocking curve of the reference SiC single crystal used in Example 2.
- FIG. 4 shows an example of Raman scattering light measurement data of a bulk SiC single crystal.
- Example 1 First, a 2 inch (55 mm diameter) 4H-type SiC single crystal ingot produced by the sublimation recrystallization method was ground on the periphery, then cut to a thickness of 0.5 mm using a multi-wire saw, and a diamond polish was used to achieve a thickness of 0. Polishing to 36 mm, and finally chemical mechanical polishing (CMP) was performed to finish the substrate.
- the surface roughness Ra was 0.1 nm.
- a 10 mm square chip was cut out from the center of the substrate to obtain a reference SiC single crystal having a thickness of 0.35 mm and a size of 10 mm ⁇ 10 mm.
- the SiC single crystal ingot from which the reference SiC single crystal is taken out has a nitrogen concentration of 6 ⁇ 10 18 to 9 ⁇ 10 18 atoms / cm 3 , and a molten alkali in the vicinity of the taken out reference SiC single crystal.
- the dislocation density was 4.8 ⁇ 10 3 / cm 2 and the number of micropipes was 0.6 / cm 2 .
- the half width was 8.3 arcsec as shown in FIG. Met.
- the 4H type SiC single crystal has a hexagonal crystal structure, and crystal planes are defined by a c-plane, a-plane, and m-plane. Therefore, in XRD measurement, X-rays are incident on a reflection surface that includes a c-axis component in the normal line, a reflection surface that also includes an a-axis component, and a reflection surface that includes an m-axis component, and the diffraction peak is analyzed.
- the lattice spacing is calculated from the angle satisfying. That is, the lattice spacing between the c planes is obtained from the Bragg condition for the c plane. Similarly, the lattice spacing between the a surfaces can be obtained from the Bragg condition for the a surface, and the lattice spacing between the m surfaces can be obtained from the Bragg condition for the m surface.
- This XRD measurement was performed under the following conditions using a high-precision X-ray diffractometer having an accuracy of 0.00001 mm.
- the X-ray source is a rotating counter cathode (copper target), and the rated output is 18 kW.
- X-ray incidence and detection were performed in parallel with the ⁇ 11-20> direction of the reference SiC single crystal. There are two measurement points, a center of the reference SiC single crystal and a position 2 mm away from the edge, and precise X-rays at three reflective surfaces ⁇ 00012 ⁇ , ⁇ 11-28 ⁇ , and ⁇ 1-1010 ⁇ .
- the polytypes of these ingots A to D are all 4H type, and have the diameter, height, and nitrogen concentration shown in Table 1 below.
- the Raman shift was measured using Raman spectroscopy as follows. First, on the first day of measurement, the Raman shift R ref is measured at the center of the reference SiC single crystal obtained above, and the Raman shift R A is measured at the center of the C plane of the ingot A. Difference (R A ⁇ R ref ) was obtained.
- the measurement day 2 with measuring the Raman shift R ref at the center of the reference SiC single crystal again measures the Raman shift R B in the center of the C plane of the ingot B, these Raman shift difference ( R B -R ref ) was determined.
- the Raman shift was measured in the same manner for the ingot C (the third day measurement) and the ingot D (the fourth day measurement), and the difference from the Raman shift R ref of the reference SiC single crystal was obtained. .
- the Raman shift was measured using a Raman spectrometer (NRS-7100 manufactured by JASCO Corporation, resolution ⁇ 0.05 cm ⁇ 1 ), and a 532 nm green laser was used as the light source. This is irradiated so that each surface of the sample (SiC single crystal for reference and ingots A to D) has a ⁇ 2 ⁇ m spot, and the focal depth is adjusted to be about 10 ⁇ m from the surface of each sample.
- the measurement light was irradiated at a spot interval of 10 ⁇ m for a total of 72 points of 8 rows ⁇ 9 rows, and the Raman shift was obtained from the average value.
- Such an ingot having a large strain can be preliminarily annealed to prevent generation of cracks in the processing step. At that time, since it is not necessary to anneal an ingot having a small distortion, it is not necessary to add extra labor and cost.
- Example 2 A 4 inch (105 mm diameter) 4H SiC single crystal ingot manufactured by sublimation recrystallization is ground and cut into a 2 mm thick sheet using a multi-wire saw. A 15 mm square square chip was cut out from approximately the center. In Example 2, the thickness was somewhat increased in consideration of handling properties. Next, both the Si surface and the C surface were polished by diamond polishing to obtain a reference SiC single crystal having a surface roughness Ra of 0.3 nm, a thickness of 1.9 mm, and a size of 15 mm ⁇ 15 mm.
- the SiC single crystal ingot from which the reference SiC single crystal was taken out has a nitrogen concentration of 4.0 ⁇ 10 19 atoms / cm 3 and is etched by molten alkali etching in the vicinity of the taken out reference SiC single crystal.
- the dislocation density was 3.7 ⁇ 10 3 / cm 2 and the number of micropipes was 0.3 / cm 2 .
- the half width was 11.9 arcsec as shown in FIG. Met.
- the obtained reference SiC single crystal was subjected to X-ray diffraction (XRD) measurement in the same manner as in Example 1 to obtain lattice constants.
- XRD X-ray diffraction
- SiC single crystal ingots E to H were prepared. These ingots were each subjected to outer peripheral grinding, and then cut into a thickness of 0.5 mm with a multi-wire saw, and 20 as-sliced substrates were produced from each ingot. Then, one as-sliced substrate was extracted from each ingot and subjected to CMP polishing to prepare four types of SiC single crystal substrates e1 to h1 shown in Table 2 as evaluation objects.
- the amount of change in warpage after epitaxial growth is higher in the order of the SiC single crystal substrate having the larger Raman shift difference. That is, the lattice distortion also means the size of the interstitial distance of the SiC single crystal, and the bimetallic effect due to the difference in interstitial distance between the epitaxial film having a low nitrogen doping concentration and the SiC single crystal substrate having a high nitrogen doping concentration. Is considered to represent warpage after epitaxial growth.
- the as-sliced substrates prepared in advance from the SiC single crystal ingots E to H were further extracted one by one, and each was subjected to CMP polishing to further prepare four types of SiC single crystal substrates e2 to h2 shown in Table 4. . Then, a Raman shift was measured for these SiC single crystal substrates e2 to h2 in the same manner as described above.
- the amount of change in warpage in the SiC single crystal substrates g2 and h2 could be suppressed.
- the remaining as-sliced substrates obtained from the SiC single crystal ingots E and F are obtained from the SiC single crystal ingots G and H with a film thickness of 30 ⁇ m during the epitaxial growth of the SiC single crystal.
- the wave number of a neon lamp is used as a reference. Strictly speaking, there are subtle fluctuations in the emission spectrum of the neon lamp itself. Therefore, by utilizing the present invention, it is possible to incorporate a reference SiC single crystal into a measurement apparatus, and to determine the Raman shift of the measurement SiC single crystal relative to the reference SiC single crystal. In other words, by making it a “reference SiC single crystal embedded type Raman spectroscopic measurement device”, it is not necessary to incorporate a neon lamp in the device, and the wave number of the neon lamp is not affected, and more accurate measurement is possible. It becomes possible to construct a Raman spectroscopic measuring apparatus having a simple structure.
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Abstract
Description
<範囲1>
10.058≦c≦10.060(Å)
3.070≦a≦3.072(Å)
2.659≦m≦2.661(Å)
<範囲2>
10.05903≦c≦10.05916(Å)
3.071114≦a≦3.071497(Å)
2.659663≦m≦2.659994(Å)
先ず、昇華再結晶法で製造した2インチ(直径55mm)の4H型SiC単結晶インゴットを外周研削した後、マルチワイヤーソーを用いて厚さ0.5mmに切断し、ダイヤモンドポリッシュにより厚さ0.36mmまで研磨して、最後に化学機械研磨(CMP)を行って基板に仕上げた。表面粗さはRaで0.1nmとした。そして、この基板の中心部から10mm角の正方形状のチップを切り出して、厚さ0.35mm、サイズ10mm×10mmの参照用SiC単結晶を得た。なお、この参照用SiC単結晶を取り出したSiC単結晶インゴットは、窒素濃度が6×1018~9×1018atoms/cm3であり、また、取り出した参照用SiC単結晶の近傍で溶融アルカリエッチングによりエッチピットの観察をしたところ、転位密度は4.8×103/cm2であり、マイクロパイプは0.6個/cm2であった。更には、この参照用SiC単結晶を取り出したSiC単結晶インゴットから切り出したウエハについて、X線ロッキングカーブの測定を行ったところ、図3(a)に示したように、半値幅は8.3arcsecであった。
昇華再結晶法で製造した4インチ(直径105mm)の4H型SiC単結晶インゴットを外周研削し、マルチワイヤーソーを用いて厚さ2mmの薄板状に切断した後、中心と円周を結ぶ半径のほぼ中央部から15mm角の正方形状のチップを切り出した。この実施例2では、取り扱い性を考慮してやや厚みのあるものとした。次いで、Si面とC面共にダイヤモンドポリッシュにより研磨して、表面粗さRaが0.3nm、厚さ1.9mm、サイズ15mm×15mmの参照用SiC単結晶を得た。なお、この参照用SiC単結晶を取り出したSiC単結晶インゴットは、窒素濃度が4.0×1019atoms/cm3であり、また、取り出した参照用SiC単結晶の近傍で溶融アルカリエッチングによりエッチピットの観察をしたところ、転位密度は3.7×103/cm2であり、マイクロパイプは0.3個/cm2であった。更には、この参照用SiC単結晶を取り出したSiC単結晶インゴットから切り出したウエハについて、X線ロッキングカーブの測定を行ったところ、図3(b)に示したように、半値幅は11.9arcsecであった。
Claims (11)
- 基準とする参照用炭化珪素単結晶のラマンシフトRrefを測定し、かつ、評価対象である複数のバルク状の炭化珪素単結晶のそれぞれのラマンシフトRnを測定して、各ラマンシフトRnと前記ラマンシフトRrefとの差分を求め、当該差分を相対比較することで、評価対象である複数のバルク状炭化珪素単結晶における格子の歪みの大小を相対的に評価することを特徴とする、バルク状炭化珪素単結晶の評価方法。
- 参照用炭化珪素単結晶が、100μm以上2000μm以下の厚みを有し、かつ、表面粗さRaが1nm以下である、請求項1に記載のバルク状炭化珪素単結晶の評価方法。
- 参照用及び評価対象の炭化珪素単結晶がいずれも4H型のポリタイプを有して、参照用炭化珪素単結晶のマイクロパイプ密度が1.0個/cm2以下であり、かつ転位密度が5×103個/cm2以下であることを特徴とする、請求項1又は2に記載のバルク状炭化珪素単結晶の評価方法。
- 参照用及び評価対象の炭化珪素単結晶がいずれも4H型のポリタイプを有して、参照用炭化珪素単結晶のX線ロッキングカーブの半値幅が15arcsec以下であることを特徴とする、請求項1又は2に記載のバルク状炭化珪素単結晶の評価方法。
- 参照用及び評価対象の炭化珪素単結晶がいずれも4H型のポリタイプを有して、参照用炭化珪素単結晶の格子定数が以下の範囲である、請求項1~4のいずれかに記載のバルク状炭化珪素単結晶の評価方法。
10.05903≦c≦10.05916(Å)
3.071114≦a≦3.071497(Å)
2.659663≦m≦2.659994(Å) - 参照用及び評価対象の炭化珪素単結晶が、いずれも昇華再結晶法により作製されたものである、請求項1~5のいずれかに記載のバルク状炭化珪素単結晶の評価方法。
- 評価対象であるバルク状の炭化珪素単結晶が、炭化珪素単結晶インゴット又は炭化珪素単結晶基板である、請求項1~6のいずれかに記載のバルク状炭化珪素単結晶の評価方法。
- 評価対象であるバルク状の炭化珪素単結晶が厚さ500μm以下の場合、水平な載置面を備えた支持台座に評価対象のバルク状炭化珪素単結晶を貼り付けて、ラマンシフトRnを測定する、請求項1~7のいずれかに記載のバルク状炭化珪素単結晶の評価方法。
- 請求項1~8のいずれかに記載の方法に用いられる参照用炭化珪素単結晶であって、サイズが5mm角以上50mm角以下であると共に厚みが100μm以上2000μm以下であり、また、表面粗さRaが1nm以下であり、かつ、マイクロパイプ密度が1.0個/cm2以下、及び転位密度が5×103個/cm2以下であることを特徴とする、バルク状炭化珪素単結晶の評価に用いられる参照用炭化珪素単結晶。
- X線ロッキングカーブの半値幅が15arcsec以下であることを特徴とする、請求項9に記載の参照用炭化珪素単結晶。
- 下記の範囲の格子定数を有することを特徴とする、請求項9又は10に記載の参照用炭化珪素単結晶。
10.05903≦c≦10.05916(Å)
3.071114≦a≦3.071497(Å)
2.659663≦m≦2.659994(Å)
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0318744A (ja) * | 1989-06-16 | 1991-01-28 | Sharp Corp | 半導体装置の結晶歪み測定方法 |
JP2001122692A (ja) * | 1999-10-26 | 2001-05-08 | Central Res Inst Of Electric Power Ind | 半導体結晶の製造方法およびこれを利用する製造装置 |
JP2005322944A (ja) * | 2005-07-08 | 2005-11-17 | Sharp Corp | 窒化ガリウム系半導体発光素子の評価方法および製造方法 |
JP2008103650A (ja) * | 2006-09-21 | 2008-05-01 | Nippon Steel Corp | SiC単結晶基板の製造方法、及びSiC単結晶基板 |
JP2011247906A (ja) * | 2011-09-12 | 2011-12-08 | Photon Design Corp | 薄膜半導体結晶層の歪み測定方法および測定装置 |
WO2013021902A1 (ja) * | 2011-08-05 | 2013-02-14 | 住友電気工業株式会社 | 基板、半導体装置およびこれらの製造方法 |
JP2013053049A (ja) * | 2011-09-06 | 2013-03-21 | Sumitomo Electric Ind Ltd | 炭化珪素基板、炭化珪素基板の製造方法、および半導体装置の製造方法 |
JP2014028757A (ja) * | 2011-08-29 | 2014-02-13 | Nippon Steel & Sumitomo Metal | 炭化珪素単結晶インゴット及びそれから切り出した基板 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0626945A (ja) | 1991-01-09 | 1994-02-04 | Sumitomo Metal Ind Ltd | 残留応力の測定方法及び該方法に使用する測定装置 |
JPH1179896A (ja) * | 1997-08-27 | 1999-03-23 | Denso Corp | 炭化珪素単結晶の製造方法 |
US6641662B2 (en) * | 1998-02-17 | 2003-11-04 | The Trustees Of Columbia University In The City Of New York | Method for fabricating ultra thin single-crystal metal oxide wave retarder plates and waveguide polarization mode converter using the same |
JP2001247906A (ja) | 1999-12-27 | 2001-09-14 | Sumitomo Special Metals Co Ltd | 鉄基磁性材料合金粉末の製造方法 |
US6756781B2 (en) * | 2001-11-15 | 2004-06-29 | Airak, Inc. | Sensor for optically measuring magnetic fields |
JP4054243B2 (ja) | 2002-10-10 | 2008-02-27 | 新日本製鐵株式会社 | 炭化珪素単結晶ウェハの製造方法、および炭化珪素単結晶ウェハ |
US7075642B2 (en) * | 2003-02-24 | 2006-07-11 | Intel Corporation | Method, structure, and apparatus for Raman spectroscopy |
US20070059501A1 (en) * | 2003-08-01 | 2007-03-15 | The New Industry Research Organization | Tantalum carbide, method for producing tantalum carbide, tantalum carbide wiring and tantalum carbide electrode |
JP4473769B2 (ja) | 2005-04-14 | 2010-06-02 | 新日本製鐵株式会社 | 炭化珪素単結晶の焼鈍方法 |
US7767022B1 (en) * | 2006-04-19 | 2010-08-03 | Ii-Vi Incorporated | Method of annealing a sublimation grown crystal |
JP4917485B2 (ja) * | 2006-10-10 | 2012-04-18 | 株式会社堀場製作所 | 応力成分測定方法 |
JP5281258B2 (ja) | 2006-10-10 | 2013-09-04 | 株式会社堀場製作所 | 応力測定方法 |
US7976629B2 (en) * | 2008-01-01 | 2011-07-12 | Adam Alexander Brailove | Crystal film fabrication |
JP5643509B2 (ja) * | 2009-12-28 | 2014-12-17 | 信越化学工業株式会社 | 応力を低減したsos基板の製造方法 |
US9658513B2 (en) * | 2012-04-20 | 2017-05-23 | Macquarie University | Device and method for converting a light and a laser system |
US20140097444A1 (en) * | 2012-10-09 | 2014-04-10 | Industrial Technology Research Institute | Nitride semiconductor device |
-
2014
- 2014-05-30 WO PCT/JP2014/064475 patent/WO2015181971A1/ja active Application Filing
- 2014-05-30 EP EP14893482.1A patent/EP3150995B1/en active Active
- 2014-05-30 KR KR1020167033237A patent/KR20170012272A/ko not_active Application Discontinuation
- 2014-05-30 CN CN201480079106.3A patent/CN106415245B/zh active Active
- 2014-05-30 JP JP2016523075A patent/JP6251804B2/ja active Active
- 2014-05-30 US US15/314,731 patent/US10048142B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0318744A (ja) * | 1989-06-16 | 1991-01-28 | Sharp Corp | 半導体装置の結晶歪み測定方法 |
JP2001122692A (ja) * | 1999-10-26 | 2001-05-08 | Central Res Inst Of Electric Power Ind | 半導体結晶の製造方法およびこれを利用する製造装置 |
JP2005322944A (ja) * | 2005-07-08 | 2005-11-17 | Sharp Corp | 窒化ガリウム系半導体発光素子の評価方法および製造方法 |
JP2008103650A (ja) * | 2006-09-21 | 2008-05-01 | Nippon Steel Corp | SiC単結晶基板の製造方法、及びSiC単結晶基板 |
WO2013021902A1 (ja) * | 2011-08-05 | 2013-02-14 | 住友電気工業株式会社 | 基板、半導体装置およびこれらの製造方法 |
JP2014028757A (ja) * | 2011-08-29 | 2014-02-13 | Nippon Steel & Sumitomo Metal | 炭化珪素単結晶インゴット及びそれから切り出した基板 |
JP2013053049A (ja) * | 2011-09-06 | 2013-03-21 | Sumitomo Electric Ind Ltd | 炭化珪素基板、炭化珪素基板の製造方法、および半導体装置の製造方法 |
JP2011247906A (ja) * | 2011-09-12 | 2011-12-08 | Photon Design Corp | 薄膜半導体結晶層の歪み測定方法および測定装置 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3150995A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019060681A (ja) * | 2017-09-26 | 2019-04-18 | クアーズテック株式会社 | 化合物半導体基板の評価方法、およびこれを用いた化合物半導体基板の製造方法 |
KR102068933B1 (ko) * | 2019-07-11 | 2020-01-21 | 에스케이씨 주식회사 | 탄화규소 잉곳 성장용 분말 및 이를 이용한 탄화규소 잉곳의 제조방법 |
US10822720B1 (en) | 2019-07-11 | 2020-11-03 | Skc Co., Ltd. | Composition for preparing silicon carbide ingot and method for preparing silicon carbide ingot using the same |
WO2022270525A1 (ja) * | 2021-06-25 | 2022-12-29 | エア・ウォーター株式会社 | 半導体素子および半導体素子の製造方法 |
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