CN103794675A - Method for forming thin layer via zero-distance material transferring and deposition - Google Patents

Method for forming thin layer via zero-distance material transferring and deposition Download PDF

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Publication number
CN103794675A
CN103794675A CN201210418424.0A CN201210418424A CN103794675A CN 103794675 A CN103794675 A CN 103794675A CN 201210418424 A CN201210418424 A CN 201210418424A CN 103794675 A CN103794675 A CN 103794675A
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temperature
matrix
material source
source
solar cell
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CN103794675B (en
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金益腾
黄群健
林川
费萨尔.艾哈迈德
辛骞骞
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First Solar Malaysia Sdn Bhd
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General Electric Co
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Priority to PCT/IB2013/059732 priority patent/WO2014064663A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02551—Group 12/16 materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
    • H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
    • H01L31/03925—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
    • H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
    • H01L31/073—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising only AIIBVI compound semiconductors, e.g. CdS/CdTe solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S50/00—Monitoring or testing of PV systems, e.g. load balancing or fault identification
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
    • H02S50/00—Monitoring or testing of PV systems, e.g. load balancing or fault identification
    • H02S50/10—Testing of PV devices, e.g. of PV modules or single PV cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/543—Solar cells from Group II-VI materials

Abstract

The invention relates to a method for forming a layer of material on a basic body. The method comprises the following steps: a material source of a semiconductor polycrystalline or amorphous material with a melting point or minimum softening temperature is contacted with the basic body; temperature difference is formed between the material source and the basic body within a time segment, wherein temperature of the material source is in a first temperature range and average temperature of the material source is a first average temperature, the temperature of the basic body is in a second temperature range and the average temperature of the basic body is a second average temperature, the first average temperature is higher than the second average temperature and lower than the melting point or the minimum softening temperature of the semiconductor polycrystalline or amorphous material so that a part of the semiconductor polycrystalline or amorphous material on the material source can be transferred to the basic body; and the material source is separated from the basic body so that the basic body with a layer of the semiconductor polycrystalline or amorphous material formed on the surface is acquired.

Description

By the lamellar method of zero distance material transfer deposition shape
Technical field
A kind of physical method and technique that forms thin layer of relate generally to of the present invention, particularly, relates to a kind of material that makes and transfers to the matrix being in contact with it from material source, to form the method for thin layer of this source material on matrix.
Background technology
At present, the chemistry of thin film deposition or physical method have a variety of, and these methods mostly need to complete by complicated technique and/or expensive equipment.For most of physical methods, such as, close-spaced sublimation method (Close Space Sublimation), reactive sputtering and molecular beam epitaxy method (MolecularBeam Epitaxy) etc., it need to operate under the environment of high temperature and high vacuum.Under these circumstances, material source and matrix all need to stand equal high temperature, and this will damage the matrix that low melting material is made.Such as, conventionally obtained by close-spaced sublimation method or reactive sputtering for the semiconductor polycrystal film layer of solar cell, in this process, matrix need stand the high temperature with material source equal extent.This just requires to use can resistant to elevated temperatures matrix, thereby causes much cheaply lightweight matrix due to cannot withstand high temperatures and cannot use.Therefore, how to allow the made matrix of some low melting materials not suffer damage in film deposition process and become a large challenge.
Therefore, need to provide a kind of new method that forms thin layer.This new method can solve matrix and face the problem that high temperature is challenged, and high temperature or cryogenic material matrix all be can be used for, such as, manufacture solar cell.
Summary of the invention
The present invention relates to a kind of method that is used for forming layer of material on matrix, the method comprises the following steps: will have the semiconductor polycrystal of fusing point or minimum softening temperature or the material source of amorphous materials and substrate contact; Make in a period of time to form between described material source and matrix a temperature difference, wherein, the temperature of described material source is in the first temperature range, its mean temperature is the first mean temperature, the temperature of described matrix is in the second temperature range, its mean temperature is the second mean temperature, described the first mean temperature is higher than described the second mean temperature, and lower than fusing point or the minimum softening temperature of described semiconductor polycrystal or amorphous materials, a part of semiconductor polycrystal or amorphous materials on described material source are transferred on described matrix; And by described material source from described matrix separately, obtain a surface deposition and be formed with the matrix of semiconductor polycrystal described in one deck or amorphous materials.
Accompanying drawing explanation
Be described for embodiments of the invention in conjunction with the drawings, the present invention may be better understood, in the accompanying drawings:
Fig. 1 (a) has shown material source and the matrix in one embodiment of the invention, and this material source and matrix are brought together and contact with each other, so that material can be transferred to matrix from material source.
Fig. 1 (b) has shown the material source shown in Fig. 1 (a) and the temperature curve of matrix.
Fig. 2 has shown material source and the matrix of putting together and contact with each other, and it is sandwiched between two enclosing covers.
Fig. 3 (a) has shown the solar cell device and the MoTe that in example one, are used as material source 2matrix.
Fig. 3 (b) has shown the state of example one seven solar cell devices used after part material is transferred to corresponding matrix.
Fig. 3 (c) has shown seven MoTe that example one is used 2the state of matrix after deposition formation one deck is from the material on corresponding solar cell device.
Fig. 4 has shown seven MoTe of described example one 2the configuration of surface of the deposited material layer forming on matrix and cross-sectional image.
Fig. 5 (a) has shown the solar cell device and the CdS matrix that in example two, are used as material source.
Fig. 5 (b) has shown three solar cell devices used in example two state after part material is transferred to corresponding matrix.
Fig. 5 (c) has shown the state of example two three CdS matrixes used after deposition formation one deck is from the material on corresponding solar cell device.
Fig. 5 (d) has shown the solar cell that has utilized respectively three CdS matrixes shown in Fig. 5 (c).
Fig. 6 has shown the efficiency of three solar cells shown in Fig. 5 (d).
Fig. 7 (a) has shown Sb used in example three 2te 3material source and as the solar cell device of matrix.
Fig. 7 (b) has shown that seven solar cell devices used in example three form one deck from corresponding Sb in deposition 2te 3sb on material source 2te 3state after material.
Fig. 7 (c) has shown seven Sb used in example three 2te 3the state of material source after part material is transferred to corresponding matrix.
Fig. 8 has shown contact sign and the battery performance of the solar cell that has used respectively seven solar cell devices shown in Fig. 7 (b).
Fig. 9 (a) has shown lead material source used in example four and the solar cell device as matrix.
Fig. 9 (b) has shown the state of example four nine solar cells used after deposition formation one deck is from the lead material on corresponding lead material source.
Embodiment
Below will be described in detail the specific embodiment of the present invention.For fear of too much unnecessary details, in following content, will known structure or function be described in detail.
The language of approximation used herein can be used for quantitative expression, shows can allow quantity to have certain variation in the situation that not changing basic function.Therefore, be not limited to this accurate numerical value itself with the numerical value that the language such as " approximately ", " left and right " are revised.In certain embodiments, " approximately " represents to allow the numerical value of its correction to change in positive and negative 10 (10%) scope, such as, what " about 100 " represented can be any numerical value between 90 to 110.In addition,, in the statement of " about the first numerical value is to second value ", revise two numerical value of the first and second numerical value approximately simultaneously.In some cases, approximation language may be relevant with the precision of measuring instrument.
In the present invention, mentioned numerical value comprises all numerical value that Yi Ge unit, a unit increases from low to high, supposes unit, at least two, interval between any lower value and high value herein.For instance, if the quantity of a component or the value of a technological parameter, such as, temperature, pressure, time etc., is from 1 to 90,20 to 80 better, 30 to 70 the bests, to want to express being set forth in this specification that 15 to 85,22 to 68,43 to 51,30 to 32 numerical value such as grade have all understood.For the numerical value that is less than 1,0.0001,0.001,0.01 or 0.1 is considered to a more suitable unit.Previous example is the use of explanation for example only, in fact, allly is all regarded as being clearly listed as in this manual in a similar manner in the minimum combinations of values between peak of enumerating.
Outside definition, technology used herein and scientific terminology have the identical meanings of generally understanding with those skilled in the art of the invention.Term used herein " first ", " second " etc. do not represent any order, quantity or importance, and just for distinguishing a kind of element and another kind of element.And " one " or " one " does not represent the restriction of quantity, but represent to exist the relevant item of.
Embodiments of the invention are transferred to the matrix contacting with this material source from material source about a kind of material that makes, to form the method for material described in one deck on this matrix.
As shown in Fig. 1 (a), make material source and substrate contact, within the regular hour, make to produce a suitable temperature difference between described material source and matrix, make the part distillation of material source and transfer to matrix from material source.The described time may be in 2 seconds to 5 minute, or further, in 20 seconds to 5 minute, or further, in the scope between 50 seconds to 5 minute.By described material source and matrix separately after, on described matrix, form the coating that one deck comprises described material.In order to obtain suitable temperature difference, to make the material transfer on material source form required coating to matrix.Described material source and matrix have a kind of temperature curve as shown in Fig. 1 (b), wherein, first temperature range at the temperature place of described material source has first mean temperature, second temperature range at the temperature place of described matrix has second mean temperature, described the first mean temperature is greater than described the second mean temperature, but is less than fusing point (for polycrystalline material) or the minimum softening temperature (for amorphous materials) of the material of described material source.
Temperature difference between described material source and matrix may be higher than a certain particular value, such as: 200 ° of C, 300 ° of C, 350 ° of C or 400 ° of C.In certain embodiments, the temperature difference between described material source and matrix between 300 ° of C to 700 ° of C, or further, between 300 ° of C to 500 ° of C.Described temperature difference can be within a certain period of time, such as in 20 seconds to 5 minute, is kept above a certain particular value.Such as, in an embodiment as shown in Fig. 1 (b), temperature difference between material source and matrix remains on above approximately 50 seconds (approximately between the 170th 220 seconds of second to the) of 200 ° of C, and wherein remains on above approximately 20 seconds (approximately between the 180th 200 seconds of second to the) of 350 ° of C.
The maximum temperature of described the first temperature range can be lower than the fusing point of the material of described material source or minimum softening temperature, or further, between 400 ° of C to 1000 ° of C, or further, between 600 ° of C to 1000 ° of C.The maximum temperature of described the second temperature range can be lower than 700 ° of C, or further, lower than 600 ° of C, or further, lower than 400 ° of C, or further, lower than 350 ° of C.The minimum temperature of described the first temperature range can be higher than the maximum temperature of described the second temperature range.Such as, in the temperature curve shown in Fig. 1 (b), the maximum temperature of described material source and matrix is about respectively 700 ° of C and 350 ° of C, and within the time period in the 110th 390 seconds of second to the, the minimum temperature of described material source is higher than the maximum temperature of matrix.
Described material source and matrix can contact with each other by plane or curved surface.In certain embodiments, as shown in Fig. 1 (a), described material source and matrix are writing board shape, contact with each other by its plane surface each other, in order to make close contact between described material source and matrix, can exert pressure to described material source and matrix, they are pressed against each other.In certain embodiments, as shown in Figure 2, described material source and matrix can be clipped between enclosing cover, can outside described, cover and exert pressure to guarantee close contact between described material source and matrix.Described enclosing cover can be used to facilitate the temperature survey of described material source and matrix.In one embodiment, temperature sensor can be connected in to described enclosing cover, be used for measuring the material source that contacts with this enclosing cover or the temperature of matrix.The good heat proof material of described enclosing cover available heat conductive performance, as graphite material is made.In a specific embodiment, described enclosing cover is carbon plate.
Temperature difference between described material source and matrix can produce with diverse ways.
In certain embodiments, described temperature difference is by the method that material source and matrix heat up with different speed is obtained.Described material source and matrix can heat by certain way, make the heating rate of material source be greater than the heating rate of matrix.Described material source or matrix, or they both can use higher than approximately 1 ° of C/s, or further, higher than approximately 5 ° of C/s, or further, heat higher than the heating rate of approximately 10 ° of C/s.Wherein, in certain embodiments, described material source can be used the heating rate heating higher than approximately 20 ° of C/s.Such as, in temperature curve as shown in Figure 1, at least, within the time period in the 170th 190 seconds of second to the, described matrix is to heat with the heating rate higher than approximately 5 ° of C/s, and described material source is to heat with the heating rate higher than approximately 20 ° of C/s.Described material source and (or) matrix carry out heat temperature raising by one or more thermals source.The example of described thermal source includes but not limited to various lamps, laser or hot wire.
In some specific embodiments, the described temperature difference can obtain in the following manner, that is, heat with a kind of thermal source that makes heat first arrive again described matrix through described material source.Described heat can arrive matrix through material source along the direction of the contact surface perpendicular to described material source and matrix.In one embodiment, can place a thermal source at the opposite side of the side with respect to matrix place of described material source, such as Halogen lamp LED etc., like this, the heat of described thermal source just can arrive matrix again by way of material source.Such as, as shown in Figure 2, described material source and matrix are sandwiched between two enclosing covers, provide heat with Halogen lamp LED, and this heat passes through enclosing cover, material source, the matrix near material source successively, then arrives the enclosing cover near matrix.
In some specific embodiments, can pass through with the independent heating material of localized heating laser source, and not add hot basal body, produce required temperature difference.In this process, described matrix, except the intensification because causing from the heat of material source, does not raise because other heat causes temperature.
In certain embodiments, described matrix can be connected on cooling system, to assist that substrate temperature is controlled to a lower level.Described cooling system can be any appropriate system of assisting matrix to be controlled at a lower temperature, such as, water-cooling system and liquid nitrogen cooling system etc.
Described material source comprises that the method that at least a portion can provide by the embodiment of the present invention transferred to the transferable material on matrix.In certain embodiments, whole described material source all uses transferable material to make, and in the time of its very thin thickness, may wholely transfer to completely on matrix.In certain embodiments, a described material source part is made up of transferable material, and a part is made up of other materials.
In practice, described material source is can being repeatedly used as the material source of different matrix before consuming completely, to form material layer in different matrix.
Described transferable material can be any solid with high vapour pressure, can be at relatively low temperature, such as, at the temperature lower than 1000 ° of C, before fusing, distil.In certain embodiments, described transferable material is semiconductor polycrystal or amorphous materials.In some specific embodiments, described transferable material is fusing point or minimum softening temperature semiconductor polycrystal or the amorphous materials lower than 2000 ° of C, can under a comparatively gentle condition, there is distillation and material transfer, thereby make the process of described material transfer have more operability.The example of described semiconductor polycrystal or amorphous materials includes but not limited to cadmium telluride (CdTe), cadmium selenide (CdSe), antimony telluride (Sb 2te 3), bismuth telluride (Bi 2te 3), lead telluride (PbTe), cadmium sulfide (CdS), selenium sulfide (SeS), zinc telluridse (ZnTe), tellurium zinc cadmium (CZT) and their combination.Because the method for the embodiment of the present invention is particularly suitable for transfer of semiconductor polycrystalline or amorphous materials, therefore herein mainly for semiconductor polycrystal or amorphous materials, be described and illustrate in particular for manufacturing solar facilities or the semiconductor polycrystal of element or the transfer of amorphous materials, but method of the present invention is not limited to this application, also can be used for other field.
Described matrix can be anyly in described material transfer process, to remain solid-stately, and the solid of gross distortion does not occur.Include but not limited to semi-conducting material, other metal and glass for the manufacture of the material of described matrix.
Owing to described matrix can being controlled at a relatively low temperature, and need not suffer the high temperature equal with material source, therefore the method for the embodiment of the present invention can form certain material layer on matrix, but without making described matrix suffer temperatures involved.This is for by the matrix made material of non-refractory, such as, with bearing the matrix that more than 5 minutes materials is made 400 ° of temperature more than C, have great importance for the manufacture of solar facilities or element.Such as, the volatile materials such as tellurium and antimony also can be survived in described material transfer process, therefore can be used to make described matrix.
Described material source and matrix can be placed in vacuum or reduced pressure atmosphere (pressure is less than conventional atmospheric environment).Atmosphere wherein can be air, oxygen, inert gas or other gas.
The method of the embodiment of the present invention is simple especially in operation, without complicated technique or expensive equipment.By form certain temperature difference on described material source and matrix, control the pressure of material source and matrix place environment, a part of material distillation on material source is also transferred on the matrix that the temperature that is in contact with it is lower by recrystallization process.The time distilling by control, can be controlled in the thickness of the material layer forming on described matrix.
In a kind of method of the embodiment of the present invention, structure and the crystallite dimension of the material layer forming are controlled.Such as, by adjusting and (or) control technological parameter, include but not limited to temperature difference and the heating rate of material source and (or) matrix etc. between material source and matrix, the material layer that can control according to specific needs formation is monocrystalline, polycrystalline or impalpable structure.In addition, crystallite dimension, if crystal grain depth-width ratio etc. is also controlled.
The method of the embodiment of the present invention will further describe by following nonrestrictive example.In these examples, available different material source and matrix test on matrix, to form the material of one deck from material source.
Example one
In this example, comprise by one that successively CdTe layer, CdS layer, cadmium mix tin-oxide (cadmiumdoped stannous oxide, CTO) layer, zinc are mixed tin-oxide (cadmium doped stannous oxide, CTO) solar cell device of layer and glassy layer is as material source, by a MoTe 2plate (for sample 1-6) or MoTe 2/ CdTe cover layer (only for sample 7) is as matrix.
As shown in Fig. 3 (a), by described solar cell device and MoTe 2plate (MoTe 2matrix) be stacked together Face to face, make CdTe layer and MoTe on solar cell device 2substrate contact, then they are clipped between two carbon plates, a laminated construction formed.Described whole lamination is placed in a vacuum heating chamber (not shown), after described solar cell device, arrives MoTe with heat 2the mode of heating heating of matrix.Work as MoTe 2the temperature of matrix is elevated to predetermined temperature with the heating rate of 5 ° of C/s left and right from room temperature, such as, after 350 ° of C, described lamination is carried out to the annealing in process of certain hour, MoTe in this process 2the temperature of matrix remains near described predetermined temperature, and the temperature rise of described solar cell device is to higher value.The temperature of described lamination can be controlled by short annealing system (rapidthermal annealing system), like this, and can be by controlling described MoTe 2the temperature of solar cell device described in the next automatic regulation and control of temperature of matrix.
For the ease of comparative analysis, by different parameters, comprise the maximum temperature that solar cell device in substrate temperature, annealing time and annealing process (material source) reaches, carry out seven tests.The concrete test parameters of described seven tests is as shown in the table:
Sample number Substrate temperature (° C) Time (minute) The maximum temperature of material source) ° C)
1 625 5 1000
2 575 5 950
3 525 5 925
4 475 3 900
5 425 3 850
6 350 2 700
7 425 3 850
Fig. 3 (b) has shown that the solar cell device in described seven tests is transferred to corresponding MoTe at its part material 2situation after on matrix.Fig. 3 (c) has shown the MoTe in described seven tests 2the situation of matrix after deposition forms the material on the self-corresponding solar cell device of one deck.As Fig. 3 (b) with 3(c), the solar cell device of sample 1 and MoTe 2matrix indicates respectively numeral " 1 ", by that analogy.For sample 1, not only the CdTe layer on solar cell device has been transferred to MoTe 2on matrix, CTO layer and the ZTO layer of CdS layer and part have also been transferred to MoTe 2on matrix, the only CTO/ZTO layer (as shown in the figure, in figure, the darker part of color is remaining CTO/ZTO layer) of remaining glassy layer and part.For sample 2-5, CdTe layer and CdS layer have moved away, also remaining CTO layer, ZTO layer and glassy layer.For sample 6, the CdTe layer of the overwhelming majority has moved away, also remaining a fraction of CdTe layer (as shown in the figure, in figure, the part of black is remaining CdTe layer) and CdS layer, CTO layer, ZTO layer and glassy layer.For sample 7, CdTe layer has moved away, also remaining CdS layer, CTO layer, ZTO layer and glassy layer.Visible, in the time that the temperature of solar cell device is enough high, CdS layer, even CTO and ZTO layer all can shift.
Fig. 4 has shown the MoTe in described seven tests respectively 2configuration of surface and the cross-sectional image of the CdTe layer forming on matrix, the picture that wherein indicates numeral " 1 " represents configuration of surface and the cross-sectional image of sample 1, by that analogy.Can find out, different tests has obtained the CdTe layer of different-thickness and structure, and in the time that substrate temperature reduces, CdTe grows up to the column structure that depth-width ratio is larger.
As shown in Figure 4, at the MoTe of sample 1 2on matrix, only there is a small amount of CdTe material, but as shown in Figure 3 (b), CdTe layer, CdS layer and most CTO and ZTO layer on the solar cell device of sample 1 disappear, therefore can infer, when the temperature of matrix reaches certain value, such as, while reaching 625 ° of C tested in sample 1, CdTe distillation is settled and is not transferred on matrix.
Example two
In this example, be similar to solar cell device used in example one with one and make material source, make matrix with chemical bath deposition CdS plate.
As shown in Fig. 5 (a), described solar cell device and chemical bath deposition CdS plate (CdS matrix) are stacked together Face to face, make CdTe layer and CdS substrate contact on solar cell device, then they are clipped between two carbon plates, form a laminated construction.Described whole lamination is placed in a vacuum heating chamber (not shown), after described solar cell device, arrives the mode of heating heating of CdS matrix with heat.When the temperature of CdS matrix with the heating rate of 5 ° of C/s left and right after room temperature is elevated to predetermined temperature, described lamination is carried out to the annealing in process of certain hour, in this process, the temperature of CdS matrix remains near described predetermined temperature, and the temperature rise of described solar cell device is to higher value.The temperature of described lamination can be controlled by short annealing system, like this, can carry out by controlling the temperature of described CdS matrix the temperature of solar cell device described in automatic regulation and control.
For the ease of comparative analysis, by different parameters, comprise the maximum temperature that in substrate temperature, annealing time and annealing process, material source reaches, carry out three tests.The concrete test parameters of described three tests is as shown in the table:
Sample number Substrate temperature (° C) Time (minute) The maximum temperature (° C) of material source
1 550 2 950
2 525 2 925
3 475 2 900
Fig. 5 (b) has shown solar cell device in described three tests situation after its part material is transferred on corresponding CdS matrix.Fig. 5 (c) has shown the CdTe material layer of the next self-corresponding solar cell device forming on the CdS matrix in described three tests.As shown in the figure, at substrate temperature lower than certain value, such as the corresponding temperature of 475 ° of C(samples 3) time, be not that whole CdTe can shift in 2 minutes.
The CdS matrix that deposits CdTe layer that described test is obtained, for the manufacture of solar cell, carries out efficiency test.Fig. 5 (d) has shown the efficiency of three solar cells of the CdS matrix manufacture utilizing respectively shown in Fig. 5 (c).The efficiency of the solar cell of the CdS matrix manufacture that deposits CdTe layer obtaining by the method for this example as shown in the figure, can reach 7.5% left and right.
Example three
In this example, with Sb 2te 3plate is made material source, is similar to solar cell device used in example one makes matrix with one.
As shown in Figure 7 (a), by described Sb 2te 3plate (Sb 2te 3material source) and described solar cell device be stacked together Face to face, make Sb 2te 3material source contacts with the CdTe layer on solar cell device, then they are clipped between two carbon plates, forms a laminated construction.Described whole lamination is placed in a heating chamber (not shown), uses heat by way of described Sb 2te 3after material source, arrive the mode of heating heating of solar cell device.When the temperature of solar cell device matrix with the heating rate of 5 ° of C/s left and right after room temperature is elevated to predetermined temperature, described lamination is carried out to the annealing in process of certain hour, in this process, the temperature of solar cell device matrix remains near described predetermined temperature, and described Sb 2te 3the temperature rise of material source is to higher value.The temperature of described lamination can be controlled by short annealing system, like this, can carry out Sb described in automatic regulation and control by the temperature of controlling described solar cell device matrix 2te 3the temperature of material source.
For the ease of comparative analysis, by different parameters, comprise Sb in atmosphere in heating chamber, substrate temperature, annealing time, annealing process 2te 3the thickness of the maximum temperature that material source reaches and material source used, has carried out seven tests.The concrete test parameters of described seven tests is as shown in the table:
Figure BDA00002315813200101
Fig. 7 (b) has shown that the solar cell device in described seven tests is formed with Sb thereon 2te 3situation after material layer.Fig. 7 (c) has shown the Sb in described seven tests 2te 3the situation of material source after part material is transferred on corresponding solar cell device.As shown in the figure, for sample 1-5, on solar cell device, formed continuous and uniform Sb 2te 3material layer.For sample 6, only has a small amount of Sb 2te 3material transfer has arrived on solar cell device.For sample 7, only have few or or even there is no a Sb 2te 3material transfer has arrived on solar cell device.
Shown in Fig. 7 (b) that described test is obtained, deposit Sb 2te 3the solar cell device of layer, for the manufacture of solar cell, carries out efficiency test.Fig. 8 has shown contact sign and the battery performance of these solar cells.As shown in Figure 8, sample 5 demonstrates diode behavior.
Example four (comparison example)
In this example, take stereotype as material source, be similar to solar cell device used in example one with one and make matrix.
As shown in Fig. 9 (a), described stereotype (lead material source) and described solar cell device are stacked together Face to face, lead material source is contacted with the CdTe layer on solar cell device, then they are clipped between two carbon plates, form a laminated construction.Described whole lamination is placed in a vacuum heating chamber (not shown), behind described lead material source, arrives the mode of heating heating of solar cell device with heat.When the temperature of solar cell device matrix with the heating rate of 5 ° of C/s left and right after room temperature rises to predetermined temperature, described lamination is carried out to the annealing in process of certain hour, in this process, the temperature of solar cell device matrix remains near described predetermined temperature, and the temperature rise in described lead material source is to higher value.The temperature of described lamination can be controlled by short annealing system, like this, can carry out by controlling the temperature of described solar cell device matrix the temperature in lead material source described in automatic regulation and control.
For the ease of comparative analysis, by different parameters, comprise the thickness of maximum temperature that in substrate temperature, annealing time, annealing process, lead material source reaches and material source used, carry out nine tests.The concrete test parameters of described nine tests is as shown in the table:
Figure BDA00002315813200111
Fig. 9 (b) has shown that the solar cell device in described nine tests deposits the situation after lead material thereon.As shown in the figure, for sample 1-5, on solar cell device, deposit a small amount of lead, but not continuous uniform of the lead layer forming.
The present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Therefore, no matter from which point, above-mentioned embodiment of the present invention all can only think explanation of the present invention can not limit the present invention, scope of the present invention is to be defined by claims, rather than defined by above-mentioned, therefore, any change in implication and the scope suitable with claims of the present invention, all should think to be included in the scope of claims.

Claims (22)

1. a method that is used for forming layer of material on matrix, the method comprises:
The semiconductor polycrystal of fusing point or minimum softening temperature or the material source of amorphous materials and substrate contact will be there is;
Make in a period of time to form between described material source and matrix a temperature difference, wherein, the temperature of described material source is in the first temperature range, the mean temperature of this first temperature range is the first mean temperature, the temperature of described matrix is in the second temperature range, the mean temperature of this second temperature range is the second mean temperature, described the first mean temperature is higher than described the second mean temperature, and lower than fusing point or the minimum softening temperature of described semiconductor polycrystal or amorphous materials, a part of semiconductor polycrystal or amorphous materials on described material source are transferred on described matrix, and
By described material source from described matrix separately, obtain a matrix at semiconductor polycrystal described in surface deposition formation one deck or amorphous materials.
2. the method for claim 1, wherein said temperature difference produces with thermal source.
3. method as claimed in claim 2, wherein said thermal source is Halogen lamp LED, laser or hot wire.
4. method as claimed in claim 2, the heat of wherein said described thermal source arrives described matrix after described material source.
5. method as claimed in claim 4, wherein said material source and matrix are clipped between two enclosing covers, and the heat of described thermal source is successively through arriving the enclosing cover near matrix near enclosing cover, material source, the matrix of material source again.
6. method as claimed in claim 2, the heating rate of wherein said material source is higher than 1 ° of C/s.
7. method as claimed in claim 2, the heating rate of wherein said matrix is higher than 1 ° of C/s.
8. the method for claim 1, wherein said matrix is connected in a cooling system.
9. the method for claim 1, the temperature difference between wherein said material source and matrix is greater than 300 ° of C.
10. the method for claim 1, the temperature difference between wherein said material source and matrix is between 300 ° of C to 500 ° of C.
11. the method for claim 1, the maximum temperature of wherein said the first temperature range is between 400 ° of C to 1000 ° of C.
12. the method for claim 1, the maximum temperature of wherein said the second temperature range is lower than 700 ° of C.
13. the method for claim 1, the maximum temperature of wherein said the second temperature range is less than 400 ° of C.
14. the method for claim 1, wherein within the described time period, and the minimum temperature of described the first temperature range is higher than the maximum temperature of described the second temperature range.
15. the method for claim 1, wherein the maximum temperature of described the first temperature range be less than fusing point or the minimum softening temperature of described semiconductor polycrystal or amorphous materials.
16. the method for claim 1, the wherein said time period is between 50 seconds to 5 minute.
17. the method for claim 1, pass through plane contact between wherein said material source and matrix.
18. the method for claim 1, the fusing point of wherein said semiconductor polycrystal or amorphous materials or minimum softening temperature are less than 2000 ° of C.
19. the method for claim 1, wherein said semiconductor polycrystal or amorphous materials are selected from cadmium telluride, antimony telluride, bismuth telluride, lead telluride, zinc telluridse, tellurium zinc cadmium, cadmium selenide, cadmium sulfide, selenium sulfide and combination thereof.
20. the method for claim 1, the material of wherein said matrix is selected from tellurium molybdenum, cadmium telluride, zinc telluridse, cadmium sulfide, glass and combination thereof.
21. the method for claim 1, the material of wherein said matrix can not bear the more than 5 minutes time under 400 ° of high temperature more than C.
22. the method for claim 1, wherein said material source and matrix are positioned over vacuum or are less than in conventional atmospheric reduced pressure atmosphere.
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CN101325156A (en) * 2008-08-04 2008-12-17 东莞宏威数码机械有限公司 Method and device for preparing polysilicon thin-film solar battery
CN102292808A (en) * 2008-11-26 2011-12-21 康宁股份有限公司 Glass-ceramic-based semiconductor-on-insulator structures and method for making the same
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