CN102169908A - Composite transparent conductive film of cadmium telluride (CdTe) solar battery and preparation method of composite transparent conductive film - Google Patents

Composite transparent conductive film of cadmium telluride (CdTe) solar battery and preparation method of composite transparent conductive film Download PDF

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Publication number
CN102169908A
CN102169908A CN2011100469491A CN201110046949A CN102169908A CN 102169908 A CN102169908 A CN 102169908A CN 2011100469491 A CN2011100469491 A CN 2011100469491A CN 201110046949 A CN201110046949 A CN 201110046949A CN 102169908 A CN102169908 A CN 102169908A
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film
conductive film
zno
transparent conductive
sno
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褚君浩
梁艳
马建华
朱晓晶
王善力
江锦春
姚娘娟
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SHANGHAI SOLAR BATTERY RESEARCH AND DEVELOPMENT CENTER
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SHANGHAI SOLAR BATTERY RESEARCH AND DEVELOPMENT CENTER
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    • Y—GENERAL 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
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Abstract

The invention discloses a composite transparent conductive film of a cadmium telluride (CdTe) solar battery and a preparation method of the composite transparent conductive film. The composite transparent conductive film consists of zinc oxide: aluminium (ZnO:Al) and zinc 2 stannic oxide 4 (Zn2SnO4) which are environment-friendly. The method comprises a step of forming the composite transparent conductive film by magnetron sputtering growth and high-temperature quick annealing treatment. The invention has the advantages that: a film material is non-toxic, rich in resources and low in cost; a Zn2SnO4 film can solve the problem of poor adhesion between an active layer and a transparent conductive film layer of the battery, can solve the problem of a too-narrow band gap of cadmium sulphide (CdS), can reduce influence of the thickness of the CdS on the performance of the battery, and can improve the quantum efficiency of the CdTe battery in a whole effective wave band; and the composite film with ZnO:Al and Zn2SnO4 structures has low resistivity and high transmissivity, and is a novel transparent conductive film applied to the CdTe solar battery.

Description

The compound transparent electricity conductive film of CdTe solar cell and preparation method
Technical field
The present invention relates to the transparent conductive oxide film technical field, specifically be meant a kind of compound transparent electricity conductive film and preparation method of the CdTe of being used for thin-film solar cells.
Background technology
The CdTe solar cell is considered to a kind of very promising thin-film solar cells.CdTe has the optical band gap of 1.45eV, very the optimum energy gap that needs near solar cell; Absorption coefficient is about 10 5Cm -1, ideally, the CdTe film that 1 μ m is thick can absorb 99% solar radiation energy, as solar cell material, can reduce the consumption of material, reduces production costs.In addition, it can utilize multiple fast filming fabrication techniques, and commerciality performance in recent years is preferable, and many researchers have an optimistic view of its market prospects, thinks that may surpass the occupancy volume of non-crystal silicon solar cell future.
CdTe battery primary structure is: substrate/transparent conductive film (TCO)/n-CdS/p-CdTe/ back electrode.Have a problem in the preparation process of CdTe battery: the main absorbed layer of sunlight is at the CdTe layer, and only be 2.4eV as the CdS film band gap of n type layer, sunlight can be absorbed most of shortwave energy through the CdS film time, for avoiding energy loss, make the sunlight CdTe of entering layer as much as possible, just need attenuate CdS layer, but the CdS layer is thin excessively, rete can be the island distribution again and be difficult for forming continuous film, causes film that micropore is arranged, and makes the direct conducting of p type CdTe and tco layer, form the pin hole effect, destroy the pn junction characteristic of battery, reduce battery efficiency, so the control of CdS thicknesses of layers is become difficult problem of holding.
Concerning the tco layer of CdTe battery, its preparation process also is a very important link, on the one hand, the TCO film is from resistivity and two cell integrated performances of aspect influence of transmissivity, and the surface topography of TCO film, lattice structure etc. also affect the performance of the CdS film each side of subsequent deposition on the other hand.In the US006137048A patent, people such as Xuanzhi Wu have announced a kind of Cd 2SnO 4/ Zn 2SnO 4The compound transparent electricity conductive film structure solves the problem of CdS film band gap and thickness with this, and the battery structure of formation is: substrate/Cd 2SnO 4/ Zn 2SnO 4/ CdS/CdTe/ back electrode.Zn wherein 2SnO 4As resilient coating, on the one hand can with the CdS thin film alloysization, form and have the more Zn of high band gap than CdS xCd 1-xThe S layer, on the other hand, CdS and Zn 2SnO 4Between the phase counterdiffusion that takes place, consumed portion C dS film, can adopt thick slightly CdS film in process of production and need not sacrifice the short-circuit current density of battery.Cd 2SnO 4Lead and high transmission rete as high electricity, though and Zn 2SnO 4Have identical crystal structure, but Cd is poisonous, the film quality of preparation is wayward, studies less at present.In addition, Cd 2SnO 4The preparation cost of target is high, and aspect industrial production, cost factor is the factor that needs emphasis to consider, therefore, and Cd 2SnO 4The feature limits of the expensive preparation of film its application in the CdTe battery industry is produced.
If we can find a kind of material can abandon poisonous, expensive Cd 2SnO 4Layer adopts and nontoxic, highly cheaply leads high transmission material and substitute, with Zn 2SnO 4The resilient coating combination, the transparent conductive film of formation two-layer composite will have the very big market prospect.
Summary of the invention
Based on the above-mentioned variety of problems of mentioning, the objective of the invention is to overcome the defective that prior art exists, a kind of compound transparent electricity conductive film that is used for the CdTe thin-film solar cells and preparation method of environmental protection proposed.
Technical scheme of the present invention is: compound transparent electricity conductive film is by ZnO:Al and Zn 2SnO 4Constitute, handle, reach our desired compound transparent electricity conductive film by magnetron sputtering growth and high temperature rapid thermal annealing.
A kind of compound transparent electricity conductive film of CdTe solar cell that is used for of the present invention is by pass through magnetron sputtering, the ZnO:Al/Zn that grows on glass substrate 2SnO 4Constitute.Wherein ZnO:Al is by Al 2O 3Mix, dopant dose is than being 1wt%～3wt%.
A kind of preparation method who is used for the compound transparent electricity conductive film of CdTe solar cell of the present invention the steps include:
A. glass substrate is cleaned up and dries up with nitrogen with conventional semiconductor technology, put on the chip bench of magnetron sputtering chamber, will be by Al 2O 3Mix, dopant dose is than being ZnO:Al target and the Zn of 1wt%～3wt% 2SnO 4Target is installed on separately the target rifle, and the sputtering chamber vacuum is evacuated to 2 * 10 -4Pa, the ZnO:Al film of on glass substrate, growing earlier then, back growth Zn 2SnO 4Film.
The magnetron sputtering parameter area of ZnO:Al rete is set: sputtering power is 100～250W, and sputter gas is a high-purity Ar, and sputtering pressure 0.1～0.3Pa, underlayer temperature are room temperature, controls film thickness in 500～1200nm scope by sedimentation time.
Zn 2SnO 4The magnetron sputtering parameter area of rete is set: sputtering power is 50W～250W, and sputter gas is high-purity O 2, sputtering pressure is 0.1～0.4Pa, underlayer temperature is a room temperature, controls film thickness in 20～100nm scope by sedimentation time.
B. with above-mentioned glass/ZnO:Al/Zn 2SnO 4The original position short annealing 5～15 minutes in the high-purity Ar atmosphere of the film of composite construction, annealing gas pressure is 1～3Pa, 500～650 ℃ of annealing temperatures naturally cool to room temperature and take out.
The most significant advantage of the present invention is:
1, adopts ZnO:Al/Zn 2SnO 4Two-layer composite can save the heating process of ZnO:Al film in preparation process, because Zn 2SnO 4Film needs 500～650 ℃ short time annealing process, allows ZnO:Al/Zn 2SnO 4Double-layer compound film is short annealing at high temperature, can promote the growth of crystal grain in the film, thereby simplifies technology, saving cost.In addition, bilayer film is annealed together, and the crystal grain in the bilayer film is grown up simultaneously, has reduced the stress between the rete, strengthens adhesive force.
2, Zn 2SnO 4Film has good thermal stability and very strong chemical resistance, can protect the ZnO:Al film to avoid the influence of high temperature and corrosion, enlarges the range of application of ZnO:Al film.
3, Zn 2SnO 4Film has very high transmissivity (see figure 1), combines with the ZnO:Al film to form composite transparent conductive film, the loss that can not bring the film integral transmissivity.
4, Zn 2SnO 4Film is as resilient coating, can with the CdS thin film alloysization, form and have the more Zn of high band gap than CdS film xCd 1-xThe S film, the short-circuit current density of increase battery.CdS and Zn 2SnO 4The phase counterdiffusion that takes place between the film can improve the adhesion problems of CdS layer and tco layer, solves the THICKNESS CONTROL problem of CdS film, also can improve the quantum efficiency of CdTe battery at whole effective wave band.
5, ZnO:Al film and Zn 2SnO 4Film has the Zn atom simultaneously, does not exist the mutual diffusion of atom between the rete to bring the deterioration problem of film quality.
Description of drawings
Fig. 1 is Zn 2SnO 4(81nm) the transmissivity collection of illustrative plates of film
Fig. 2 is ZnO:Al (683nm)/Zn 2SnO 4(81nm) the transmissivity collection of illustrative plates of two-layer compound transparent conductive film
Fig. 3 is ZnO:Al (1006nm)/Zn 2SnO 4(54nm) the transmissivity collection of illustrative plates of two-layer compound transparent conductive film
Embodiment
Embodiment 1:
Glass substrate is cleaned up and dry up, put on the chip bench of magnetron sputtering chamber with nitrogen.With ZnO:Al target (Al 2O 3Dopant dose is than being 2wt%) and Zn 2SnO 4Target is installed on separately the target rifle, and the sputtering chamber vacuum is evacuated to 2 * 10 -4Pa adopts radiofrequency magnetron sputtering technology growth ZnO:Al film earlier, back growth Zn then on glass substrate 2SnO 4Film.
The magnetron sputtering parameter area of ZnO:Al rete is set: sputtering power is 200W, and sputter gas is a high-purity Ar, and sputtering pressure 0.15Pa, underlayer temperature are room temperature, sedimentation time 1.5 hours, and obtaining film thickness is 683nm.
Zn 2SnO 4The magnetron sputtering parameter area of rete is set: sputtering power is 100W, and sputter gas is high-purity O 2, sputtering pressure is 0.33Pa, and underlayer temperature is a room temperature, and the long-pending time is 1.5 hours, and obtaining film thickness is 81nm.Is 600 ℃ of original position short annealings 8 minutes in the high-purity Ar atmosphere of 2Pa with the film of this composite construction at air pressure, naturally cools to room temperature and takes out.
Fig. 2 has shown ZnO:Al (683nm)/Zn of embodiment 1 2SnO 4(81nm) double-layer compound film transmissivity collection of illustrative plates, as seen from Figure 2, this laminated film reached for 82% (comprising substrate) in the visible light wave range transmissivity, and also had high transmissivity near infrared band, and laminated film resistivity can reach 1.6 * 10 -3Ω cm.
Embodiment 2:
Glass substrate is cleaned up and dry up, put on the chip bench of magnetron sputtering chamber with nitrogen.With ZnO:Al target (Al 2O 3Dopant dose is than being 2wt%) and Zn 2SnO 4Target is installed on separately the target rifle, and the sputtering chamber vacuum is evacuated to 2 * 10 -4Pa adopts radiofrequency magnetron sputtering technology growth ZnO:Al film earlier, back growth Zn then on glass substrate 2SnO 4Film.
The magnetron sputtering parameter area of ZnO:Al rete is set: sputtering power is 250W, and sputter gas is a high-purity Ar, and sputtering pressure 0.15Pa, underlayer temperature are room temperature, sedimentation time 2 hours, and obtaining film thickness is 1006nm.
Zn 2SnO 4The magnetron sputtering parameter area of rete is set: sputtering power is 100W, and sputter gas is high-purity O 2, sputtering pressure is 0.33Pa, and underlayer temperature is a room temperature, and the long-pending time is 1 hour, and obtaining film thickness is 54nm.Is 600 ℃ of original position short annealings 8 minutes in the high-purity Ar atmosphere of 2Pa with the film of this composite construction at air pressure, naturally cools to room temperature and takes out.
Fig. 3 has shown ZnO:Al (1006nm)/Zn of embodiment 2 2SnO 4(54nm) double-layer compound film transmissivity collection of illustrative plates, as seen from Figure 3, this laminated film reached for 80% (comprising substrate) in the visible light wave range transmissivity, and also had high transmissivity near infrared band, and laminated film resistivity can reach 7.86 * 10 -4Ω cm.

Claims (2)

1. the compound transparent electricity conductive film of a CdTe solar cell, it is characterized in that: this compound transparent electricity conductive film is by the ZnO:Al/Zn that grows on glass substrate by magnetron sputtering 2SnO 4Constitute, wherein ZnO:Al is by Al 2O 3Mix, dopant dose is than being 1wt%～3wt%.
2. the preparation method of the compound transparent electricity conductive film of a CdTe solar cell is characterized in that step is:
A. glass substrate is cleaned up and dries up with nitrogen with conventional semiconductor technology, put on the chip bench of magnetron sputtering chamber, will be by Al 2O 3Mix, dopant dose is than being ZnO:Al target and the Zn of 1wt%～3wt% 2SnO 4Target is installed on separately the target rifle, and the sputtering chamber vacuum is evacuated to 2 * 10 -4Pa, the ZnO:Al film of on glass substrate, growing earlier then, back growth Zn 2SnO 4Film;
The magnetron sputtering parameter area of ZnO:Al rete is set: sputtering power is 100～250W, and sputter gas is a high-purity Ar, and sputtering pressure 0.1～0.3Pa, underlayer temperature are room temperature, controls film thickness in 500～1200nm scope by sedimentation time;
Zn 2SnO 4The magnetron sputtering parameter area of rete is set: sputtering power is 50W～250W, and sputter gas is high-purity O 2, sputtering pressure is 0.1～0.4Pa, underlayer temperature is a room temperature, controls film thickness in 20～100nm scope by sedimentation time;
B. with above-mentioned glass/ZnO:Al/Zn 2SnO 4The original position short annealing 5～15 minutes in the high-purity Ar atmosphere of the film of composite construction, annealing gas pressure is 1～3Pa, 500～650 ℃ of annealing temperatures naturally cool to room temperature and take out.
CN2011100469491A 2011-02-25 2011-02-25 Composite transparent conductive film of cadmium telluride (CdTe) solar battery and preparation method of composite transparent conductive film Pending CN102169908A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107638879A (en) * 2017-11-09 2018-01-30 合肥师范学院 A kind of method for preparing multilevel hierarchy Ag ZnO films and its multilevel hierarchy Ag ZnO films of preparation
CN109346560A (en) * 2018-11-27 2019-02-15 江苏拓正茂源新能源有限公司 A kind of preparation method of solar battery core

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107638879A (en) * 2017-11-09 2018-01-30 合肥师范学院 A kind of method for preparing multilevel hierarchy Ag ZnO films and its multilevel hierarchy Ag ZnO films of preparation
CN107638879B (en) * 2017-11-09 2020-09-25 合肥师范学院 Method for preparing multi-level structure Ag-ZnO film and multi-level structure Ag-ZnO film prepared by method
CN109346560A (en) * 2018-11-27 2019-02-15 江苏拓正茂源新能源有限公司 A kind of preparation method of solar battery core

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Application publication date: 20110831