CN113188983A - Deviation<100>Crystal orientation 9oDislocation density measuring method for germanium single crystal wafer - Google Patents
Deviation<100>Crystal orientation 9oDislocation density measuring method for germanium single crystal wafer Download PDFInfo
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- CN113188983A CN113188983A CN202110437604.2A CN202110437604A CN113188983A CN 113188983 A CN113188983 A CN 113188983A CN 202110437604 A CN202110437604 A CN 202110437604A CN 113188983 A CN113188983 A CN 113188983A
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000013078 crystal Substances 0.000 title claims abstract description 49
- 229910052732 germanium Inorganic materials 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000012360 testing method Methods 0.000 claims abstract description 29
- 238000005260 corrosion Methods 0.000 claims abstract description 16
- 230000007797 corrosion Effects 0.000 claims abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007864 aqueous solution Substances 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000004364 calculation method Methods 0.000 claims description 4
- 238000005498 polishing Methods 0.000 abstract description 3
- 235000012431 wafers Nutrition 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 4
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000001739 density measurement Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- -1 copper nitrate hydrofluoric acid nitrate Chemical compound 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light
- G01N17/006—Investigating resistance of materials to the weather, to corrosion, or to light of metals
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- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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- Pathology (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Testing Or Measuring Of Semiconductors Or The Like (AREA)
Abstract
The invention discloses a dislocation density measuring method of a 9-degree germanium single crystal wafer deviated from a <100> crystal orientation, which comprises the following steps: the volume ratio of the hydrofluoric acid to the nitric acid to the copper nitrate aqueous solution is 1: 2.8-3.2: 1.8-2.2; and (3) corrosion: placing the germanium polishing sheet in a flower basket, placing the flower basket in corrosive liquid for 5-10min, taking out the flower basket, and washing with deionized water; spin-drying: putting the flower basket into a spin-drying machine, wherein the spin-drying speed is 800-; observing the surface dislocation appearance of the corroded germanium polished wafer by using a metallographic microscope, arranging a certain number of test ranges with the square side length of 13mm on the surface of the germanium polished wafer, selecting one test point in each test range, counting the number of dislocations of each test point, and calculating the dislocation density of each test point; the dislocation shape of the germanium single crystal wafer with the angle of 9 degrees deviated from the <100> crystal orientation can be clearly displayed.
Description
Technical Field
The invention relates to a semiconductor material, in particular to a dislocation density measuring method of a 9-degree germanium single crystal wafer deviated from a <100> crystal orientation.
Background
The rapid development of the aerospace industry has increasingly increased the demand for space solar cells and the quality requirements are higher and higher. Despite the continuous efforts, the silicon solar cell has been gradually replaced by the gallium arsenide solar cell in the field of space application due to its low conversion efficiency and weak radiation resistance. The gallium arsenide solar cell has high conversion efficiency, good high-temperature characteristic and radiation resistance characteristic, is more suitable for space complex environment, and has become a mainstream power supply of a spacecraft. The germanium material has the lattice constant and the thermal expansion coefficient similar to those of gallium arsenide material, has the characteristics of high mechanical strength, good radiation resistance and the like, and is the most ideal substrate material of the current gallium arsenide solar cell. At present, the crystal orientation requirement of a germanium single crystal wafer substrate material for a solar cell is that the <100> crystal orientation is closest to <111>9 +/-1 degrees, the crystal orientation deviation degree of a germanium sample wafer is required to be less than 6 degrees in a national standard GB/T5252 and 2006 germanium single crystal dislocation corrosion pit density measurement method, a corrosion detection method is not available for detecting the deviation of the germanium single crystal wafer from the <100> crystal orientation to 9-degree dislocation, and the existing dislocation corrosion pit density measurement method has the condition of large deviation after multiple measurements because the germanium dislocation is unevenly distributed on the germanium single crystal wafer. Therefore, the dislocation morphology (as shown in fig. 4) of the polished germanium single crystal with the corrosion angle of 9 degrees deviated from the <100> crystal orientation by the existing national standard method is not clear.
Disclosure of Invention
In view of the problems in the prior art, the invention provides a dislocation density measuring method of a germanium single crystal wafer which is 9 degrees away from a <100> crystal orientation. The method can clearly display the dislocation morphology of the germanium single crystal by providing a novel proportioning method of the germanium dislocation corrosive liquid (as shown in figure 5). According to the invention, from practice, according to the factors influencing the dislocation corrosion of the germanium single crystal deviating from the <100> crystal orientation by a certain angle, the dislocation of the germanium single crystal deviating from the <100> crystal orientation by 9 degrees can be clearly and obviously displayed by changing the formula of the corrosive liquid and the corrosion conditions, and a more accurate calculation method of the dislocation corrosion pit density is provided.
The technical scheme adopted by the invention is as follows: a dislocation density measuring method of a 9-degree germanium single crystal wafer deviated from a <100> crystal orientation is characterized by comprising the following steps: the method comprises the following steps:
(1) and cutting a sample wafer which is 9 degrees deviated from the <100> crystal orientation from the head and the tail of the pre-used germanium single crystal rod to prepare a germanium polished wafer.
(2) Preparing dislocation corrosive liquid, wherein the volume ratio of hydrofluoric acid to nitric acid to copper nitrate aqueous solution is 1: (2.8-3.2): (1.8-2.2).
(3) Placing the germanium polished wafer in a flower basket, and placing the flower basket in dislocation corrosion liquid, wherein the corrosion time is 5-10min and the temperature is 10-20 ℃.
(4) Taking out the flower basket, washing the flower basket by using deionized water, and putting the flower basket into a spin-drying machine, wherein the spin-drying speed is 800-.
(5) Observing the surface dislocation appearance of the corroded germanium polished section by using a metallographic microscope, arranging a certain number of test ranges with the length of a lattice side of 13mm on the surface of the germanium polished section, selecting a test point in each test range, counting dislocations of each test point, and calculating the dislocation density of the test point, wherein the calculation formula is as follows:
in the formula: n is a radical ofi: the number of dislocation in the view field;
c: a microscope coefficient;
n: number of test points
Nd: dislocation density.
The concentration of the copper nitrate aqueous solution is 10%, the concentration of the hydrofluoric acid is 40%, and the concentration of the nitric acid is 65%.
Compared with the prior art, the invention has the advantages and beneficial effects that: the dislocation appearance of the germanium sheet is very clear, the corrosion temperature range is wide, the operation is convenient, and the point taking range of the germanium dislocation density measuring method is wider and more accurate than that of the existing method.
Drawings
FIG. 1 is a layout diagram of the test point of 100mm germanium sheet according to the present invention;
FIG. 2 is a layout diagram of a test point of a 125mm germanium wafer according to the present invention;
FIG. 3 is a layout diagram of the test point of the 150mm germanium wafer according to the present invention;
FIG. 4 is a dislocation diagram of a germanium wafer using the national standard etching method of the present invention;
FIG. 5 is a dislocation pattern of a germanium wafer utilizing the present etching method of the invention.
Detailed Description
The invention is further illustrated by the following figures and examples.
By adopting the method, firstly, the dislocation density test ranges of 9-degree germanium single crystal wafers with different specifications and deviating from the <100> crystal orientation are arranged: as shown in fig. 1, 32 dislocation density test ranges of the germanium single crystal wafer with 100mm deviation from the <100> crystal orientation by 9 degrees are arranged; as shown in fig. 2, 52 dislocation density test ranges of the germanium single crystal wafer with 125mm deviation from the <100> crystal orientation by 9 degrees are arranged; as shown in fig. 3, 89 dislocation density test ranges of the germanium single crystal wafer with 150mm deviation of 9 degrees from the <100> crystal orientation are arranged.
Example (b): the dislocation density of the germanium single crystal wafer with the crystal orientation of 9 degrees deviated from the <100> by 150mm is measured as follows:
(1) and cutting a sample wafer which is 9 degrees deviated from the <100> crystal orientation from the head and the tail of the pre-used germanium single crystal rod to process the sample wafer into a germanium polished wafer (the process of processing the polished wafer is a conventional processing technology).
(2) Preparing dislocation corrosive liquid, wherein aqueous solution of hydrofluoric acid, nitric acid and copper nitrate is 1:3:2 in volume ratio.
(3) Placing the germanium polished wafer in a flower basket, and placing the flower basket in dislocation corrosive liquid, wherein the corrosion time is 8min and the temperature is 15 ℃;
(4) taking out the flower basket, washing the flower basket by using deionized water, putting the flower basket into a spin-drying machine, and drying at a drying speed: 1000r/min, and the drying time is 3 min;
(5) observing the surface dislocation appearance of the corroded germanium polished wafer by using a metallographic microscope, wherein the test range is shown in figure 3, the side length of a square grid is 13mm, each test range is provided with one test point, the dislocation density of 89 test points is calculated, and the calculation formula is as follows:
c (microscope coefficient) 105;
nd (dislocation density): 242 pieces/cm2。
The reaction mechanism of the method is as follows: the germanium polishing sheet is firstly oxidized into GeO in a copper nitrate hydrofluoric acid nitrate corrosion system2. The reaction formula is as follows: ge + HNO3+Cu(NO3)2→GeO2+CuO+NO↑+H2O。GeO2And CuO is dissolved by HF to achieve the effect of corrosion and polishing and show dislocation, in the system, nitric acid is used as an oxidizing agent, hydrofluoric acid is used as a complexing agent, and H required by oxidation is used+Substantially all from HNO3Of (2) ionization, HNO3Large amount, fast and complete oxidation rate, H+The increase of the amount of the catalyst inhibits the ionization of HF, the solution contains more HF, and GeO is generated by oxidation2Complexing with HF at any time to generate soluble complex, peeling layer by layer, and adding Cu in copper nitrate+The dislocation is reduced, the dislocation is displayed more clearly, and the appearance of the corroded dislocation is more obvious and easy to observe. The dislocation corrosion reaction is completed by oxidation reaction and dissolution reaction together, and the two reactions need to reach dynamic balance to achieve the best effect of corroding dislocation.
Claims (2)
1. A dislocation density measuring method of a 9-degree germanium single crystal wafer deviated from a <100> crystal orientation is characterized by comprising the following steps: the method comprises the following steps:
(1) cutting a sample wafer which is 9 degrees deviated from the <100> crystal orientation from the head and the tail of the pre-used germanium single crystal rod to prepare a germanium polished wafer;
(2) preparing dislocation corrosive liquid, wherein the volume ratio of hydrofluoric acid to nitric acid to copper nitrate aqueous solution is 1: (2.8-3.2): (1.8-2.2);
(3) placing the germanium polished wafer in a flower basket, and placing the flower basket in dislocation corrosive liquid, wherein the corrosion time is 5-10min and the temperature is 10-20 ℃;
(4) taking out the flower basket, washing the flower basket by using deionized water, and putting the flower basket into a spin-drying machine, wherein the spin-drying speed is 800-;
(5) observing the surface dislocation appearance of the corroded germanium polished section by using a metallographic microscope, arranging a certain number of test ranges with the length of a lattice side of 13mm on the surface of the germanium polished section, selecting a test point in each test range, counting dislocations of each test point, and calculating the dislocation density of the test point, wherein the calculation formula is as follows:
in the formula: n is a radical ofi: the number of dislocation in the view field;
c: a microscope coefficient;
n: the number of the test points is determined;
nd: dislocation density.
2. The method for measuring dislocation density of the single crystal germanium wafer at an angle of 9 degrees deviated from the <100> crystal orientation according to claim 1, is characterized in that: the concentration of the copper nitrate aqueous solution is 10%, the concentration of the hydrofluoric acid is 40%, and the concentration of the nitric acid is 65%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114088707A (en) * | 2021-10-27 | 2022-02-25 | 安徽光智科技有限公司 | Method for detecting crystal orientation defect of ultra-high pure germanium single crystal <100> |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101655427A (en) * | 2009-09-04 | 2010-02-24 | 中国电子科技集团公司第四十六研究所 | Dislocation corrosion detecting method of single germanium wafer |
| CN103698339A (en) * | 2013-12-29 | 2014-04-02 | 云南北方驰宏光电有限公司 | Crystal dislocation corrosion detection method |
| CN106567079A (en) * | 2016-09-23 | 2017-04-19 | 中锗科技有限公司 | Corrosive liquid for detecting dislocation of monocrystalline germanium slices and corrosion method |
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- 2021-04-22 CN CN202110437604.2A patent/CN113188983A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101655427A (en) * | 2009-09-04 | 2010-02-24 | 中国电子科技集团公司第四十六研究所 | Dislocation corrosion detecting method of single germanium wafer |
| CN103698339A (en) * | 2013-12-29 | 2014-04-02 | 云南北方驰宏光电有限公司 | Crystal dislocation corrosion detection method |
| CN106567079A (en) * | 2016-09-23 | 2017-04-19 | 中锗科技有限公司 | Corrosive liquid for detecting dislocation of monocrystalline germanium slices and corrosion method |
Non-Patent Citations (2)
| Title |
|---|
| 国家标准化管理委员会: "《锗单晶位错密度的测试方法》", 30 June 2020, pages: 1 - 7 * |
| 机械工业部仪器仪表工业局: "《宝石轴承测量》", 机械工业出版社, pages: 320 - 322 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114088707A (en) * | 2021-10-27 | 2022-02-25 | 安徽光智科技有限公司 | Method for detecting crystal orientation defect of ultra-high pure germanium single crystal <100> |
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