CN103996748A - Process for preparing textured ZAO transparent conductive film - Google Patents

Process for preparing textured ZAO transparent conductive film Download PDF

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Publication number
CN103996748A
CN103996748A CN201410222578.1A CN201410222578A CN103996748A CN 103996748 A CN103996748 A CN 103996748A CN 201410222578 A CN201410222578 A CN 201410222578A CN 103996748 A CN103996748 A CN 103996748A
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film
zao
etching
acetic acid
transparent conductive
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CN201410222578.1A
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王晓晶
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王晓晶
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1884Manufacture of transparent electrodes, e.g. TCO, ITO
    • H01L31/1888Manufacture of transparent electrodes, e.g. TCO, ITO methods for etching transparent electrodes
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022408Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/02Details
    • H01L31/0224Electrodes
    • H01L31/022466Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
    • H01L31/022483Electrodes made of transparent conductive layers, e.g. TCO, ITO layers composed of zinc oxide [ZnO]
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/02Details
    • H01L31/0236Special surface textures
    • H01L31/02366Special surface textures of the substrate or of a layer on the substrate, e.g. textured ITO/glass substrate or superstrate, textured polymer layer on glass substrate
    • 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 provides a process for preparing a textured ZAO transparent conductive film. The process includes the following step that the ZAO thin is etched through an acetic acid solution, wherein the concentration of acetic acid is 1%, and etching time is 10+/-3s. According to the process, the acetic acid solution with weak acidity serves as an etching solution to etch the TPT flexible base ZAO transparent conductive film, so that the film has the good textured structure and the good photoelectric property.

Description

A kind of preparation technology of texture ZAO transparent conductive film
Technical field
The present invention relates to solar cell material preparing technical field, relate in particular to a kind of preparation technology of texture ZAO transparent conductive film.
Background technology
TCO material forms transparent contact electrode for light entrance face in solar cell, for before shady face back reflection layer to improve the optical characteristics of battery and to form diffusion barrier.Matte TCO particularly goes up in lining type thin film solar cell and has important function at thin film solar cell, not only as the front electrode extracted current of battery, also as light, fall into the absorption that layer improves light in solar cell active layer simultaneously, and then raising battery current and battery efficiency, for amorphous silicon film battery, can also reduce S-W photo attenuation effect, improve stability test.The surface of ZAO film prepared by magnetron sputtering method is more smooth, need to utilize corrosive liquid to carry out surface etch, forms matte.Utilize hydrochloric acid solution to carry out report prepared by ZnO transparent conductive film matte more].But organic flexible substrate cannot be born acid stronger hydrochloric acid solution corrosion, therefore, the existing technique with acid etching is to be improved.
Summary of the invention
The object of the invention is to solve the defect that above-mentioned prior art exists, a kind of preparation technology of texture ZAO transparent conductive film is provided.
A preparation technology for texture ZAO transparent conductive film, comprising: adopt acetic acid solution corrosion ZAO film.
Further, the preparation technology of texture ZAO transparent conductive film as above, described acetic acid concentration is 1%, etch period is 10 ± 3s.
It is etching liquid that the present invention utilizes acid weak acetic acid solution, the flexible base ZAO of TPT transparent conductive film is carried out to the process conditions of etching, and film has good suede structure and photoelectric properties.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the ZAO film of etching under different acetic acid concentrations;
Fig. 2 is the average grain size of the film surface that calculates according to Scherrer formula;
Fig. 3 is the square resistance curve of the ZAO film of different acetic acid concentration etchings;
Fig. 4 is transmitance and the reflectance curve of the ZAO film of different acetic acid concentration etchings;
Fig. 5 is the absorption curves of the ZAO film of different acetic acid concentration etchings;
Fig. 6 is the XRD figure of the ZAO film prepared the different etching time;
Fig. 7 is the average grain size curve of the ZAO film prepared the different etching time;
Fig. 8-a is the SEM figure of not etching ZAO film suede structure;
Fig. 8-b is the SEM figure of etch period ZAO film suede structure while being 10s;
Fig. 8-c is the SEM figure of etch period ZAO film suede structure while being 20s;
Fig. 9 is the square resistance curve of the ZAO film of same etch period;
Figure 10 is light transmission rate and the reflectance curve of different etching time ZAO film;
Figure 11 is the absorption curves of different etching time ZAO film.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below technical scheme in the present invention be clearly and completely described, obviously, described embodiment is the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
Experimental technique:
In the present invention, adopt the method preparation of wet etching erosion after sputter to have suede structure ZAO transparent conductive film, acetic acid is etching solution, has studied different etching liquid concentration, the impact of different etching time on the ZAO film photoelectric performance of preparing on flexible TPT substrate.Specific experiment parameter is as shown in table 1:
Table 1 etching experimental technique parameter
Utilize the pH value of acetic acid solution of three kinds of concentration that PH test paper measures between 2~4, along with the increase of acetic acid concentration, pH value reduces.
Matte ZAO membrane structure and performance study
Matte ZAO structure and performance evaluation prepared by different acetic acid concentrations
Fig. 1 is the X-ray diffractogram of the ZAO film of etching under different acetic acid concentrations, and Fig. 2 is the average grain size of the film surface that calculates according to Scherrer formula.As seen from the figure, all film samples are all that 34.20 ° of left and right have strong diffraction maximum at 2 θ, and (002) crystal face of corresponding ZnO crystal, illustrates that film is wurtzite structure, and has obvious c-axis preferred orientation.Along with the increase of acetic acid concentration, (002) diffraction maximum has the trend moving to the larger angle of diffraction, and the halfwidth of diffraction maximum increases simultaneously, and average grain size reduces, and crystalline quality reduces.This may cause due to the reason of two aspects, and the one, in the Al of grain boundaries atom, be etched away, lattice constant reduces, so the angle of diffraction moves to larger direction; The 2nd, etching rear film thickness reduction, and after etching, there is more grain boundary defects, crystalline quality reduces.
Fig. 3 is the square resistance curve of the ZAO film of different acetic acid concentration etchings.As seen from the figure, the square resistance of matte ZAO film increases along with the increase of acetic acid concentration, and electric conductivity reduces along with the increase of etching concentration.In this and film, defect increases, and crystalline quality reduces relevant.After etching, the increase of grain boundaries defect, crystal boundary trap will be caught charged carriers, and carrier concentration will reduce; On the other hand, the reduction of film crystallite dimension, increases the number of grain boundaries in film, and crystal boundary scattering increases, and also can cause the reduction of film mobility, so the electric conductivity of etching rear film reduces.The square resistance of the ZAO film of etching is not minimum, and its sheet resistance is 120 Ω/.
Mean transmissivity and the reflectivity of the ZAO film of the different acetic acid concentration etchings of table 2
Fig. 4 and Fig. 5 are respectively transmitance, reflectivity and the absorption curves of the ZAO film sample of different acetic acid concentration etchings, and test spectral scope is 350-1100nm.Table 5-2 is mean transmissivity and reflectivity and the variation thereof of sample in visible-range.From Fig. 4 and table 2, the mean transmissivity of ZAO film in visible-range is 76-58%, and reflectivity is 32-14%, and the transmitance of film and all progressively reductions along with the increase of acetic acid concentration of reflectivity.This is because rough surface any direction all scattering of light can occur, before changing direction, repeatedly launched on film surface the reverberation of air-film interface, every secondary reflection back reflection rate becomes lower, therefore the surface of the final luminance factor surface smoothing of etching rear film is low, transmitance reduces with the increase of acetic acid concentration, may be because etching causes the increase of defect and the increase of surface roughness in the deterioration, film of thin film crystallization quality, and then causing that light scattering increases, transmitance reduces.As shown in Figure 5, the absorption curve that different etching liquid concentration obtains sample overlaps substantially, and the absorbance in visible-range is less than 0.5.As can be seen here, the absorbent properties of different ZAO films in visible-range are basic identical.Known according to the situation of change of reflectivity and transmitance, the roughness of the matte ZAO film forming after over etching increases with etching concentration, and film strengthens along with the increase of etching concentration scattering of light ability.
Matte ZAO membrane structure and performance evaluation prepared by the different etching time
Fig. 6 is the X-ray diffractogram of the matte ZAO film prepared the different etching time, and Fig. 7 is the average grain size of the sample that calculates according to Scherrer formula.As seen from the figure, all film samples are all between 34.16-34.28 °, to have the diffraction maximum of the last one at 2 θ, corresponding to (002) crystal face of ZnO structure, illustrate that film is wurtzite structure, and have obvious c-axis preferred orientation.Along with the increase of etch period, (002) diffraction maximum has the trend moving to the larger angle of diffraction, and the halfwidth broadening of diffraction maximum, this means that the crystalline quality of ZAO film reduces simultaneously.This variation tendency is similar on the impact of etching ZAO film with corrosion concentration, and the increase along with etching degree is all described, the crystallite dimension of ZAO film reduces, crystalline quality variation.
In order better to understand the surface texture of ZAO film after acetic acid etching, we have carried out sem test to the sample segment of preparation, and result is as shown in Fig. 8 (a)-(c).From Fig. 8 (a), can find out, the surface of ZAO film prepared by magnetron sputtering is more smooth, and after suitable etching (10s), the surface of film is by texturing, surface has formed pyramid structure (as Fig. 8 (b)), and this contributes to light to fall into the realization of function.But oversize when etch period, while reaching 20s, ZAO film is by heavy corrosion, and a lot of holes (as Fig. 8 (c)) have appearred in surface.Utilize the good light scattering function matte TCO film that has of commercially producing of realizing prepared by the technology of aumospheric pressure cvd (APCAD) also to there is similar structure.Can find out, magnetron sputtering is prepared ZAO film, and the etching through suitable, can obtain the suede structure with good light scattering ability.
Fig. 9 is the square resistance curve of the ZAO film of different etching time.As seen from the figure, along with the increase of etch period, the square resistance of film is increased to 1050 Ω/ by 120 Ω/.This may be because after etching, the reduction of thin film crystallization degree and thickness causes.Etching has negative effect to the electrical property of ZAO film, and these may be due to two reasons: the one, because the reduction of ZAO thin film crystallization quality after etching, the 2nd, because the defect that etching causes increases.Defect can be caught conduction charge carrier, and carrier concentration reduces, and causes square resistance to increase.
Figure 10 and Figure 11 are light transmission rate curve, reflectance curve and the absorption curve figure of sample within the scope of 350-1100nm of preparation.Table 3 is sample mean transmissivity and reflectivity and variations thereof in visible-range, and mean transmissivity is 78-57%, and reflectivity is between 32-23%.Transmitance and reflectivity all progressively reduce along with the increase of etch period.The absorbance curves that the different etching time obtains sample overlaps substantially, and the absorbance in visible-range is less than 0.5.Known according to the situation of change of reflectivity and transmitance, the matte ZAO film forming after over etching strengthens along with the increase of etch period scattering of light ability.The pyramid structure that this should form owing to etching rear film surface.In addition, because surface roughness increases, light is in film surface generation diffuse reflection and scattering, and film transmitance reduces.
Mean transmissivity and the reflectivity of table 3 different etching time ZAO film
The present invention adopts acetic acid solution corrosion ZAO film, successfully prepares the matte ZAO film with light trapping effect.System research acetic acid concentration and the impact of etch period on ZnO structure of transparent conductive film and photoelectric properties, Main Conclusions is as follows:
(1) certain density acetic acid solution corrosion ZAO film, does not change the crystal structure of film, and can form the surface with pyramid structure, increases roughness and the light scattering ability of film.
(2) experimental result shows, when acetic acid concentration is 1%, when etch period is 10s left and right, film has good suede structure and photoelectric properties.After etching, the transmitance of ZAO film in visible ray is about 60%, and square resistance is 260 Ω/ left and right.
(3) when acetic acid concentration is too low or etch period is too short, plane ZAO film prepared by sputter can not obtain good etching, and film surface can not form effective light trapping structure.
(4) when acetic acid concentration is too high or etch period is long, plane ZAO film is by overetch, and a lot of holes have appearred in film surface, have a strong impact on the electric conductivity of film.
Finally it should be noted that: above embodiment only, in order to technical scheme of the present invention to be described, is not intended to limit; Although the present invention is had been described in detail with reference to previous embodiment, those of ordinary skill in the art is to be understood that: its technical scheme that still can record aforementioned each embodiment is modified, or part technical characterictic is wherein equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.

Claims (2)

1. a preparation technology for texture ZAO transparent conductive film, is characterized in that, comprising: adopt acetic acid solution corrosion ZAO film.
2. the preparation technology of texture ZAO transparent conductive film according to claim 1, is characterized in that, described acetic acid concentration is 1%, and etch period is 10 ± 3s.
CN201410222578.1A 2014-05-26 2014-05-26 Process for preparing textured ZAO transparent conductive film Pending CN103996748A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101562216A (en) * 2009-05-27 2009-10-21 南开大学 Method for preparing textured ZnO membrane with pyramid-like structure
CN101572279A (en) * 2009-06-10 2009-11-04 南开大学 High mobility textured structure IMO/ZnO composite film grown by sputtering method and application thereof to solar cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101562216A (en) * 2009-05-27 2009-10-21 南开大学 Method for preparing textured ZnO membrane with pyramid-like structure
CN101572279A (en) * 2009-06-10 2009-11-04 南开大学 High mobility textured structure IMO/ZnO composite film grown by sputtering method and application thereof to solar cell

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王晓晶: "柔性基ZnO:Al透明导电薄膜材料的制备与性能研究", 《 中国博士学位论文全文数据库》, 15 September 2011 (2011-09-15), pages 93 - 99 *

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