CN102544230A - Method for growing variable forbidden bandwidth cadmium (Cd1)-x zinc (Zn) x tellurium (Te) film - Google Patents

Method for growing variable forbidden bandwidth cadmium (Cd1)-x zinc (Zn) x tellurium (Te) film Download PDF

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Publication number
CN102544230A
CN102544230A CN2012100399239A CN201210039923A CN102544230A CN 102544230 A CN102544230 A CN 102544230A CN 2012100399239 A CN2012100399239 A CN 2012100399239A CN 201210039923 A CN201210039923 A CN 201210039923A CN 102544230 A CN102544230 A CN 102544230A
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China
Prior art keywords
film
czt
sublimation
energy
tellurium
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CN2012100399239A
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Inventor
王林军
徐闰
贡伟明
汤敏燕
徐海涛
黄健
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Priority to CN2012100399239A priority Critical patent/CN102544230A/en
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention relates to a method for producing a cadmium (Cd1)-x zinc (Zn) x tellurium (Te) (CZT) film, which belongs to the field of an inorganic nonmetal material device manufacturing technology. The method for producing the CZT film adopts a Cdl-xZnxTe polycrystal or monocrystal disc which is doped with a small amount of Zn (x is smaller than 1%) as a sublimation source, and uses a close-spaced-sublimation method to directly produce the x (50%) Cdl-xZnxTe film. The CZT film is adopted to produce a top absorbing layer of a laminated solar battery, so the development of the solar battery which is low in cost and has high conversion efficiency is benefited, and meanwhile, the CdZnTe film also can be applied to a high energy particle detector.

Description

A kind of Cd of the variable energy gap of growing 1-xZn xThe method of Te film
Technical field
The present invention relates to a kind of Cd of the variable energy gap of growing 1-xZn xThe method of Te film belongs to the fabricating parts in inorganic non-metal field.
Background technology
The energy is the important substance basis that human civilization is rely and developed.The world today, along with reducing day by day and human continuous increase to energy demand of earth resource, energy crisis is extremely urgent.For survival and development, the mankind must seek to substitute the reproducible clean new forms of energy of conventional energy resource, wherein first-selected solar power generation.Solar energy has and stores hugely, never exhausted, cleanliness without any pollution, does not receive advantage such as region restriction, is human most important new forms of energy.Utilize the photovoltaic effect of solar cell to generate electricity, become the most important mode that the solar energy scale is utilized.
At present solar cell mainly comprises crystal silicon cell and thin-film solar cells, good output under the thin-film solar cells Yin Gaowen wherein, and weaknesses is good; Pollute few; Help environmental protection, energy output is high, and plasticity is good; The production materials are few, and advantages such as low price become the development trend of solar-energy photo-voltaic cell.But the conversion efficiency of current film battery assembly is also lower, and the laboratory peak efficiency of wherein the highest CIGS (CIGS) battery is 19.9% and efficient that volume production is gone up in industry just 13.1%.In order further to improve the efficient of this thin-film solar cells, can realize through the binode laminated cell.Promptly let the short light of wavelength absorbed by the wide gap material battery of top layer, the long energy transmissive of wavelength enters to let than the utilization of low energy gap width material cell, thereby to greatest extent luminous energy is become electric energy, improves conversion efficiency.Think that in the world using energy gap is the bottom cell that the CIGS material of 0.9 eV is done lamination solar cell, and the energy gap of corresponding top cell ideal material should be for about 1.6eV.To this, everybody broad research mainly be Cd 1-xZn xTe (CZT) film, its energy gap can be adjustable continuously between 1.45 (CdTe)~2.26eV (ZnTe) with not coexisting of Zn content.And the CdZnTe film of mixing Zn10% (at.%) also can be done Detector for High Energy Particles.At present; Mainly adopt the near space sublimed method to prepare the CdTe film in the world then with the magnetically controlled sputter method ZnTe film of on the CdTe film, growing; Then film is annealed; Like this at the CZT of generation at the interface of CdTe/ZnTe film, the technology more complicated of this method growth CdZnTe film, and also Zn content is not easy control in the CZT film.Also there is research group to adopt Cd 1-xZn xThe Te powder is attempted the Cd that grows for the near space sublimation source 1-xZn xThe Te film adopts x to be 0.7 Cd to the maximum even discover 1-xZn xThe Te source also can't grow x greater than 0.1 Cd 1-xZn xThe Te film.Therefore the present invention proposes to adopt the Cd that mixes a small amount of Zn (x is less than 1%) 1-xZn xTe polycrystalline or monocrystalline disk are done sublimation source, under high vacuum, directly prepare x with the near space sublimed method<50% Cd 1-xZn xThe Te film.
Summary of the invention
Content of the present invention is to adopt CdZnTe polycrystalline or the monocrystalline disk of mixing a small amount of Zn4% (at.%) to do sublimation source; Directly prepare the absorbed layer of CZT film with the near space sublimed method as solar cell; Along with Zn content in the CZT film of the variation of underlayer temperature growth can change; Thereby the CZT film that can prepare different energy gaps, this can provide a kind of new material and new technology for the thin-film solar cells of preparation high conversion efficiency.
The present invention is characterized in the CZT film that obtains among the present invention, the CZT film that adopts better simply prepared to go out the higher different energy gaps of Zn ratio is done the absorbed layer of solar cell.
For achieving the above object, the present invention adopts following technical proposals and step:
With transparent conducting glass (SnO 2: F) put on the sample stage of near space distillation depositing device, deposit the CZT film in the above; Earlier sublimation chamber is evacuated to 5Pa before the deposit film with vacuum pump; Sublimation source is for mixing the CdZnTe crystal disk of Zn 4% (at.%); 650 ° of C of sublimation source temperature, 300~500 ° of C of sample substrate temperature, cavity air pressure is 1 Pa~10KPa; The distillation time is 30 minutes, can realize that finally x is the Cd of 5%-50% 1-xZn xThe controllable deposition of Te film.
The present invention compares with prior art, has following remarkable advantage:
(1) CZT thin-film solar cells of the present invention; Employing is mixed CdZnTe polycrystalline or the monocrystalline crystal disk of Zn 4% (at.%) as sublimation source; Easy to operate with our homemade CdZnTe crystal list source growth CZT thin-film technique, only need regulate just can the grow CZT film of change energy gap of underlayer temperature.
(2) change the sample substrate temperature from 300 ° of C to 500 ° of C; Make Zn doping from 8.5% to 45.8% (at.%) in the film; Can generate energy gap 1.5eV and change to the CZT film about 1.7eV, and the less Cd of Zn is mixed in the use of present international research institution 1-xZn xThe Te powder is done sublimation source, is difficult to prepare Zn content greater than 10% CZT film.The CZT film of the high Zn content that we prepare is fit to do the top layer absorbed layer of laminated cell very much, thereby improves the photoelectric conversion efficiency of CIGS/CZT overlapping thin film solar battery.This process also can be applicable to film CdZnTe Detector for High Energy Particles simultaneously.
Description of drawings
Fig. 1: the CZT film X-ray diffractogram for preparing under the various substrate.
Fig. 2: 300 ℃ of the scanning electron microscope diagrams (a) of the CZT film for preparing under the various substrate, (b) 400 ℃, (c) 450 ℃, (d) 500 ℃.
Embodiment
After instance of the present invention specifically being described at present.
Embodiment 1:
With transparent conducting glass (SnO 2: F) put on the sample stage of near space distillation depositing device, deposit the CZT film in the above; Earlier with vacuum pump sublimation chamber is evacuated to 5Pa before the deposit film, sublimation source is to mix the Cd of a small amount of Zn 1-xZn xTe monocrystalline disk, x=4% wherein, 650 ° of C of source temperature, 500 ° of C of sample substrate temperature, cavity air pressure is 10Pa, the distillation time is 30 minutes.Calculate through measuring, the energy gap of this film is 1.7eV.
Embodiment 2:
With transparent conducting glass (SnO 2: F) put on the sample stage of near space distillation depositing device, deposit the CZT film in the above; Earlier with vacuum pump sublimation chamber is evacuated to 5Pa before the deposit film, sublimation source is to mix the Cd of a small amount of Zn 1-xZn xTe monocrystalline disk, x=4% wherein, 650 ° of C of source temperature, 450 ° of C of sample substrate temperature, cavity air pressure is 10Pa, the distillation time is 30 minutes.Calculate through measuring, the energy gap of this film is 1.6eV.
Embodiment 3:
With transparent conducting glass (SnO 2: F) put on the sample stage of near space distillation depositing device, deposit the CZT film in the above; Earlier with vacuum pump sublimation chamber is evacuated to 5Pa before the deposit film, sublimation source is to mix the Cd of a small amount of Zn 1-xZn xTe monocrystalline disk, x=4% wherein, 650 ° of C of source temperature, 400 ° of C of sample substrate temperature, cavity air pressure is 10Pa, the distillation time is 30 minutes.Calculate through measuring, the energy gap of this film is 1.53eV.
Embodiment 4:
With transparent conducting glass (SnO 2: F) put on the sample stage of near space distillation depositing device, deposit the CZT film in the above; Earlier with vacuum pump sublimation chamber is evacuated to 5Pa before the deposit film, sublimation source is to mix the Cd of a small amount of Zn 1-xZn xTe monocrystalline disk, x=4% wherein, 650 ° of C of source temperature, 300 ° of C of sample substrate temperature, cavity air pressure is 10Pa, the distillation time is 30 minutes.Calculate through measuring, the energy gap of this film is 1.5eV.
Table 1: the Zn content and the energy gap of the CZT film for preparing under the various substrate
Underlayer temperature (℃) 300 400 450 500
X value (%) 8.51 13.64 26.62 45.8
Energy gap (eV) 1.5 1.53 1.6 1.7

Claims (1)

  1. One kind the growth variable energy gap Cd 1-xZn xThe method of Te film, this method has following technical process:
    With transparent conducting glass SnO 2: F puts on the sample stage of near space distillation depositing device, deposits Cd in the above 1-xZn xThe Te film; Earlier sublimation chamber is evacuated to 5Pa before the deposit film with vacuum pump; The Cd of a small amount of Zn is mixed in employing 1-xZn xTe polycrystalline or monocrystalline disk are done sublimation source, x=4% wherein, and 550-650 ° of C of sublimation source temperature, 300~500 ° of C of sample substrate temperature, cavity air pressure is lower than 10 Pa, and the distillation time is 30 minutes, can realize that finally x is the Cd of 5%-50% 1-xZn xThe controllable deposition of Te film.
CN2012100399239A 2012-02-22 2012-02-22 Method for growing variable forbidden bandwidth cadmium (Cd1)-x zinc (Zn) x tellurium (Te) film Pending CN102544230A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103343389A (en) * 2013-07-05 2013-10-09 上海大学 Preparation method for CdZnTe film with cylindrical structure
CN104952977A (en) * 2015-05-15 2015-09-30 欧贝黎新能源科技股份有限公司 Manufacturing method of inorganic thin film solar cell
CN105161565A (en) * 2015-06-29 2015-12-16 上海大学 CdZnTe photoelectric detector comprising graphene transition layer, and preparation method for CdZnTe photoelectric detector
CN108456847A (en) * 2015-09-14 2018-08-28 北京师范大学 The method of DLC films deposited and CZT semiconductor detectors on polycrystalline CZT
CN110148627A (en) * 2019-04-28 2019-08-20 上海大学 CZT film composite material and preparation method thereof with metal buffer layer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102234765A (en) * 2010-04-23 2011-11-09 昆明物理研究所 Preparation method of target material for growing tellurium cadmium mercury film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102234765A (en) * 2010-04-23 2011-11-09 昆明物理研究所 Preparation method of target material for growing tellurium cadmium mercury film

Non-Patent Citations (1)

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Title
袁研研等: "CSS法制备CdZnTe薄膜时衬底温度的影响规律", 《功能材料》, vol. 42, no. 5, 31 October 2011 (2011-10-31), pages 890 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103343389A (en) * 2013-07-05 2013-10-09 上海大学 Preparation method for CdZnTe film with cylindrical structure
CN104952977A (en) * 2015-05-15 2015-09-30 欧贝黎新能源科技股份有限公司 Manufacturing method of inorganic thin film solar cell
CN105161565A (en) * 2015-06-29 2015-12-16 上海大学 CdZnTe photoelectric detector comprising graphene transition layer, and preparation method for CdZnTe photoelectric detector
CN108456847A (en) * 2015-09-14 2018-08-28 北京师范大学 The method of DLC films deposited and CZT semiconductor detectors on polycrystalline CZT
CN108456847B (en) * 2015-09-14 2019-11-01 北京师范大学 The method of DLC films deposited and CZT semiconductor detector on polycrystalline CZT
CN110148627A (en) * 2019-04-28 2019-08-20 上海大学 CZT film composite material and preparation method thereof with metal buffer layer

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Application publication date: 20120704