CN100477295C - Method for processing surface oxidation film of mercury cadmium telluride film material - Google Patents
Method for processing surface oxidation film of mercury cadmium telluride film material Download PDFInfo
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- CN100477295C CN100477295C CNB2006100270383A CN200610027038A CN100477295C CN 100477295 C CN100477295 C CN 100477295C CN B2006100270383 A CNB2006100270383 A CN B2006100270383A CN 200610027038 A CN200610027038 A CN 200610027038A CN 100477295 C CN100477295 C CN 100477295C
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Abstract
The invention is a Te-Cd-Hg film surface oxide film treating process, rinsing Te-Cd-Hg film with acetone, anhydrous alcohol and deionized water, corroding with bronmine and anhydrous alcohol, making surface treatment with lactic acid and alycol solution, and thus able to obtain Te-Cd-Hg surface with a very small quantity of oxides, even without oxides. And it can largely improve photoelectric performance, yield, and reliability of Te-Cd-Hg photovolt detector array, and the whole process is simple, and easy to operate, having good repeatability and strong practicality and basically does no harm to human body. And it can be widely applied to preparation of Te-Cd-Hg surfaces and making of Te-Cd-Hg photoelectric devices.
Description
Technical field
The present invention relates to the treatment process of mercury cadmium telluride thin film material surface oxidation film layer, be specifically related to adopt the metal organic-matter chemical vapor deposition method, and the treatment process of the mercury cadmium telluride thin film material surface oxidation film layer of molecular beam epitaxial method growth, this technology is mainly used in optoelectronic areas such as infra-red material and Infrared Detectors.
Background technology
Because the mercury cadmium telluride thin film material has character such as superior optics, magnetics, electricity, thereby is widely used in the photoelectric device, especially is applied to the infrared detector array of high-performance infrared imaging system.And the mercury cadmium telluride photovoltaic detector array is the core of infrared focal plane device, therefore, how to prepare the plane of crystal that satisfies the requirement of high-performance Infrared Detectors effectively, is the problem that the researcher explores for many years always.In the manufacturing process of cadmium-telluride-mercury infrared detector, require the in addition strict control of the surface of this narrow bandgap semiconductor material, make the surface have uniform stoicheiometry, no crystal defect, few surface oxidation and other surface contaminations.Because mercury cadmium telluride is a ternary-alloy material, in process of surface treatment, be easy to cause the stoicheiometry uneven surfaces, as chemical segregation and cadmium deficiency appear, and also make the surface produce oxidation film layer and defective easily, finally be difficult to obtain stoicheiometry evenly and the smooth finish surface of non-oxidation.In with insulation or the passivation technology of semi-insulating medium as passivation layer, the surface oxide layer of mercury cadmium telluride not only influences interfacial characteristics, and directly has influence on the dielectric property of passivation layer, finally influences photoelectric properties, rate of finished products, the reliability of detector array.Usually adopt bromine and methanol solution to carry out surface treatment at present, but make the surface produce " tangerine peel " problem easily.Simultaneously, methyl alcohol is bigger to people's eyes infringement, and long-term contact will cause eyes blind.For this reason, the researcher seeks for many years always and can prepare the surface treatment method that satisfies the requirement of high-performance Infrared Detectors effectively.People have carried out exploring and research (Y.Nemirovsky, et., J.Vac.Sci.Techno1., 1989, A7 (2), 450-459 to different mercury cadmium telluride surface treatment methods; J.P.Ziegler, et., 1989, A7 (2), 469-473; Hao-xin Yuan, et., Opt.Eng., 1993,32 (3), 365-371), but do not find a kind of comparatively desirable processing method yet.
Summary of the invention
Problem to be solved by this invention is: the surface oxidation film treatment process that a kind of mercury cadmium telluride thin film material is provided, use the method, make treated mercury cadmium telluride thin film material not only have the surface of uniform stoicheiometry, bright and clean, no crystal defect, and has a few even oxide-free mercury cadmium telluride surface of oxide, highly beneficial to the photoelectric properties, rate of finished products, the reliability that improve the mercury cadmium telluride photovoltaic detector array, whole technical process is simple, and is easy to operate, practical.
The treatment process of mercury cadmium telluride thin film material surface oxidation film layer comprises the mercury cadmium telluride thin film material is carried out clean; Corrosion treatment and surface treatment; It is characterized in that:
A, elder generation carry out clean to the mercury cadmium telluride thin film material:
A, in acetone soln, soaked 2～3 minutes;
B, in absolute ethyl alcohol, soaked 1～2 minute;
Cleaned 1～2 minute in c, the deionized water at room temperature;
D, dry up with high pure nitrogen (99%).
B, again the mercury cadmium telluride thin film material is carried out corrosion treatment:
A, with the mercury cadmium telluride thin film material that dries up with bromine and ethanol solution corrosion, the volume ratio of bromine and ethanol solution is (0.005～0.05): 1, etching time is 10～60 seconds, and ceaselessly rocks the mercury cadmium telluride thin film material in corrosion process;
B, in absolute ethyl alcohol, cleaned 1～2 minute.
C, at last the mercury cadmium telluride thin film material is carried out surface treatment:
A, the mercury cadmium telluride thin film material is immersed lactic acid and ethylene glycol solution, the volume ratio of lactic acid and ethylene glycol solution is (0.03～0.1): 1, in solution, soaked 1～2 minute;
B, subsequently the mercury cadmium telluride thin film material was cleaned 1～2 minute with absolute ethyl alcohol;
C, washed 1～2 minute with washed with de-ionized water again;
D, dry up with high pure nitrogen at last.
Use the treatment process of mercury cadmium telluride thin film material surface oxidation film layer of the present invention, reduce or remove the oxide on mercury cadmium telluride surface, can improve photoelectric properties, rate of finished products and the reliability of mercury cadmium telluride photovoltaic detector array greatly by surface treatment.Particularly quality and the effect to improving the mercury cadmium telluride surface passivation will play a key role.Whole technical process is simple, and is easy to operate, and good reproducibility is practical, and human body is not had injury substantially, can be widely used in the preparation on mercury cadmium telluride surface and the manufacturing of mercury cadmium telluride photoelectric device.
Description of drawings
Fig. 1 is the photoelectron spectroscopy of the tellurium (Te3d) gathered of mercury cadmium telluride thin film material surface that the present invention handles;
Fig. 2 is the photoelectron spectroscopy of the cadmium (Cd3d) gathered of mercury cadmium telluride thin film material surface that the present invention handles;
Fig. 3 is the photoelectron spectroscopy of the mercury (Hg4f) gathered of mercury cadmium telluride thin film material surface that the present invention handles;
Fig. 4 is the photoelectron spectroscopy of the oxygen (O1s) gathered of mercury cadmium telluride thin film material surface that the present invention handles;
Fig. 5 is the electron channelling pattern of the mercury cadmium telluride thin film material surface handled of the present invention.
Te3d among Fig. 15/2Only have one unimodal, show the surface almost the tellurium of non-oxidation state occur. To the Cd3d among the figure Analyze with Hg4f spectrum and to draw, because the chemical shift of Hg and Cd is minimum, illustrate that the HgCdTe surface contains Hg and Cd Oxide less. In order to determine the chemical composition on surface, with Gaussian O1s is carried out match, the O1s Gaussian is intended Closing curve only has a single peak position to exist, and matched curve overlaps fully with empirical curve, and the combination of peak position can be 532.6 EV, it shows corresponding to lip-deep oxygen physisorption (such as hydrogen-oxygen or carbon-family of oxygen group), in the detection limit scope, the tellurium cadmium The surperficial oxide-free of mercury thin-film material exists. Electron channelling pattern after processing as can be seen from Figure 5 is than the contrast before processing Obviously improve, the number of high order line is showed increased also. This be because after processing the oxide on HgCdTe surface is reduced with Remove, thereby the HgCdTe surface topography is improved.
Embodiment
Mercury cadmium telluride (the Hg that following examples are selected
1-xCd
xTe) thin-film material is the thin-film material of growing by molecular beam epitaxial method on tellurium zinc cadmium (CdZnTe) substrate, and the stoicheiometry of material is x=0.208mol.
Embodiment 1
A, elder generation soaked in acetone soln 2～3 minutes, put into absolute ethyl alcohol again and soaked 1～2 minute, cleaned in the deionized water at room temperature 1～2 minute subsequently, dried up with high pure nitrogen;
B, with the mercury cadmium telluride thin film material that dries up with bromine and ethanol solution corrosion, the volume ratio of bromine and ethanol solution is 0.005: 1, etching time is 60 seconds, and ceaselessly rocks the mercury cadmium telluride thin film material in corrosion process; Be placed on then and clean 1～2 minute in the absolute ethyl alcohol;
C, the mercury cadmium telluride thin film material is immersed lactic acid and ethylene glycol solution immediately, the volume ratio of lactic acid and ethylene glycol solution is 0.03: 1, in solution, soaked 2 minutes, subsequently the mercury cadmium telluride thin film material was cleaned 1～2 minute with absolute ethyl alcohol, used washed with de-ionized water again 1～2 minute, and dried up with high pure nitrogen at last.
A, elder generation soaked in acetone soln 2～3 minutes, put into absolute ethyl alcohol again and soaked 1～2 minute, cleaned in the deionized water at room temperature 1～2 minute subsequently, dried up with high pure nitrogen;
B, with the mercury cadmium telluride thin film material that dries up with bromine and ethanol solution corrosion, the volume ratio of bromine and ethanol solution is 0.007: 1, etching time is 50 seconds, and ceaselessly rocks the mercury cadmium telluride thin film material in corrosion process; Be placed on then and clean 1～2 minute in the absolute ethyl alcohol;
C, the mercury cadmium telluride thin film material is immersed lactic acid and ethylene glycol solution immediately, the volume ratio of lactic acid and ethylene glycol solution is 0.05: 1, in solution, soaked for 90 seconds, subsequently the mercury cadmium telluride thin film material was cleaned 1～2 minute with absolute ethyl alcohol, used washed with de-ionized water again 1～2 minute, and dried up with high pure nitrogen at last.
Embodiment 3
A, elder generation soaked in acetone soln 2～3 minutes, put into absolute ethyl alcohol again and soaked 1～2 minute, cleaned in the deionized water at room temperature 1～2 minute subsequently, dried up with high pure nitrogen;
B, with the mercury cadmium telluride thin film material that dries up with bromine and ethanol solution corrosion, the volume ratio of bromine and ethanol solution is 0.01: 1, etching time is 30 seconds, and ceaselessly rocks the mercury cadmium telluride thin film material in corrosion process; Be placed on then and clean 1～2 minute in the absolute ethyl alcohol;
C, the mercury cadmium telluride thin film material is immersed lactic acid and ethylene glycol solution immediately, the volume ratio of lactic acid and ethylene glycol solution is 0.08: 1, in solution, soaked for 70 seconds, subsequently the mercury cadmium telluride thin film material was cleaned 1～2 minute with absolute ethyl alcohol, used washed with de-ionized water again 1～2 minute, and dried up with high pure nitrogen at last.
Embodiment 4
A, elder generation soaked in acetone soln 2～3 minutes, put into absolute ethyl alcohol again and soaked 1～2 minute, cleaned in the deionized water at room temperature 1～2 minute subsequently, dried up with high pure nitrogen;
B, with the mercury cadmium telluride thin film material that dries up with bromine and ethanol solution corrosion, the volume ratio of bromine and ethanol solution is 0.03: 1, etching time is 30 seconds, and ceaselessly rocks the mercury cadmium telluride thin film material in corrosion process; Be placed on then and clean 1～2 minute in the absolute ethyl alcohol;
C, the mercury cadmium telluride thin film material is immersed lactic acid and ethylene glycol solution immediately, the volume ratio of lactic acid and ethylene glycol solution is 0.1: 1, in solution, soaked 1 minute, subsequently the mercury cadmium telluride thin film material was cleaned 1～2 minute with absolute ethyl alcohol, washed 1～2 minute with washed with de-ionized water again, dry up with high pure nitrogen at last.
Embodiment 5
A, elder generation soaked in acetone soln 2～3 minutes, put into absolute ethyl alcohol again and soaked 1～2 minute, cleaned in the deionized water at room temperature 1～2 minute subsequently, dried up with high pure nitrogen;
B, with the mercury cadmium telluride thin film material that dries up with bromine and ethanol solution corrosion, the volume ratio of bromine and ethanol solution is 0.05: 1, etching time is 10 seconds, and ceaselessly rocks the mercury cadmium telluride thin film material in corrosion process; Be placed on then and clean 1～2 minute in the absolute ethyl alcohol;
C, the mercury cadmium telluride thin film material is immersed lactic acid and ethylene glycol solution immediately, the volume ratio of lactic acid and ethylene glycol solution is 0.1: 1, in solution, soaked 1 minute, subsequently the mercury cadmium telluride thin film material was cleaned 1～2 minute with absolute ethyl alcohol, washed 1～2 minute with washed with de-ionized water again, dry up with high pure nitrogen at last.
Utilize x-ray photoelectron spectroscopy respectively measurement, analysis to be carried out in the mercury cadmium telluride surface through above-mentioned PROCESS FOR TREATMENT.The result shows that in the detection limit scope, the surface of mercury cadmium telluride thin film material has only oxygen physisorption, and surperficial oxide-free exists, and further specifies and adopts treatment process of the present invention, can obtain the mercury cadmium telluride surface of the few even non-oxidation of oxide.
Whole technical process is simple, and is easy to operate, and good reproducibility is practical, and human body is not had injury substantially, can be widely used in the preparation on mercury cadmium telluride surface and the manufacturing of mercury cadmium telluride photoelectric device.
Claims (1)
1. the treatment process of mercury cadmium telluride thin film material surface oxidation film layer comprises the mercury cadmium telluride thin film material is carried out clean; Corrosion treatment and surface treatment; It is characterized in that:
A) earlier the mercury cadmium telluride thin film material is carried out clean:
A) in acetone soln, soak 2～3 minutes;
B) in absolute ethyl alcohol, soak 1～2 minute;
C) cleaned in the deionized water at room temperature 1～2 minute;
D) dry up with high pure nitrogen,
B) again the mercury cadmium telluride thin film material is carried out corrosion treatment:
A) the mercury cadmium telluride thin film material that dries up is corroded with bromine and ethanol solution, the volume ratio of bromine and ethanol solution is (0.005～0.05): 1, and etching time is 10～60 seconds, and ceaselessly rocks the mercury cadmium telluride thin film material in corrosion process;
B) in absolute ethyl alcohol, clean 1～2 minute,
C) at last the mercury cadmium telluride thin film material is carried out surface treatment:
A) the mercury cadmium telluride thin film material is immersed lactic acid and ethylene glycol solution, the volume ratio of lactic acid and ethylene glycol solution is (0.03～0.1): 1, in solution, soaked 1～2 minute;
B) subsequently the mercury cadmium telluride thin film material was cleaned 1～2 minute with absolute ethyl alcohol;
C) washed 1～2 minute with washed with de-ionized water again;
D) dry up with high pure nitrogen at last.
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| CN101640231B (en) * | 2009-09-04 | 2012-08-29 | 中国电子科技集团公司第十一研究所 | Mesa passivation method of infrared two-color HgCdTe detector |
| CN103022246B (en) * | 2012-11-30 | 2015-02-18 | 中国科学院上海技术物理研究所 | Substrate removing technology for tellurium cadmium mercury detector based on selective wet etching process |
| CN107481921B (en) * | 2017-07-31 | 2019-11-26 | 中国电子科技集团公司第十一研究所 | A kind of cleaning method of molecular beam epitaxy substrate material |
| CN109638111A (en) * | 2018-12-19 | 2019-04-16 | 中国电子科技集团公司第十研究所 | A kind of method of infrared detector surface treatment |
| CN113113285B (en) * | 2021-03-09 | 2023-04-28 | 中国电子科技集团公司第十一研究所 | Surface cleaning method for mercury cadmium telluride chip before passivation |
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Non-Patent Citations (2)
| Title |
|---|
| Study on surface oxidative characterization of LPE HgCdTeepilayer by X-rayphotoelectron spectroscopy. Yi Li, Xinjian Yi, Liping Cai.International Journal of Infrared and Millimeter Waves,Vol.21 No.1. 2000 |
| Study on surface oxidative characterization of LPE HgCdTeepilayer by X-rayphotoelectron spectroscopy. Yi Li, Xinjian Yi, Liping Cai.International Journal of Infrared and Millimeter Waves,Vol.21 No.1. 2000 * |
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