CN104659124B - A kind of solar battery obsorbing layer material and preparation method thereof - Google Patents
A kind of solar battery obsorbing layer material and preparation method thereof Download PDFInfo
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- CN104659124B CN104659124B CN201510054369.5A CN201510054369A CN104659124B CN 104659124 B CN104659124 B CN 104659124B CN 201510054369 A CN201510054369 A CN 201510054369A CN 104659124 B CN104659124 B CN 104659124B
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Abstract
The present invention provides a kind of solar battery obsorbing layer material and preparation method thereof, belongs to solar photoelectric absorbed layer material, field of semiconductor materials.The present invention combines the rare earth resources advantage of China, uses rare earth element to replace In and prepares solar battery obsorbing layer material C u (InxX1‑x)Se2, wherein X is rare earth element, prepares solar battery obsorbing layer material C u (In especially with rare earth element yttrium (Y) doping/replacement In and GaxY1‑x)Se2.The present invention can reduce Cu (InxGa1‑x)Se2The usage amount of dissipated metal In and Ga in solar cell material, improves CuInSe simultaneously2It is the energy gap of absorbed layer material, adds the matching of sunshine spectral response, improve Cu (InxX1‑x)Se2The transformation efficiency of solar cell.
Description
Technical field
The present invention relates to solar photoelectric absorbed layer material, field of semiconductor materials, particularly relate to a kind of sun
Energy battery obsorbing layer material and preparation method thereof.
Background technology
Along with the development of human society, energy resource consumption increases day by day, non-renewable energy resources such as oil, coal etc.
Reserves increasingly exhausted make the whole world be faced with the most serious energy shortage problem, so to new forms of energy especially
It is that the exploitation of green alternative energy source has become as the problem that current mankind is in the urgent need to address.Solar energy is a kind of
Free of contamination regenerative resource, reserves are huge, widely distributed, sustainable use, and therefore solar energy is beyond doubt
The first-selection of the human future energy.
Solar cell refers to utilize photoelectric effect to make the radiated photons energy of the sun by semiconductor substance light
Electricity converting material is changed into the device of electric energy.The kind of solar cell is a lot, is divided into according to material requested:
Crystal silicon solar energy battery, silicon-based film solar cells, compound semiconductor thin film solar cell and dye
Material sensitization TiO2 nano-film solar cell.The various practical sun is considered from cost, efficiency etc.
Energy battery product, being hopeful to develop into can large-scale application as monocrystalline silicon, polysilicon solar cell
Surely belong to there is no that photoelectric efficiency attenuating effect, conversion ratio be higher, the simple CIS of good stability, technique
(CuInSe2, CIS) is solar cell.But, the energy gap of current CuInSe2 is only 1.01eV,
And containing substantial amounts of dissipated metal In in material.For the problems referred to above, research and development doping or replacement In
New material is the direction of solar cell material research.CuInSe2 doped and substituted mainly has at present
Cu(In1-xGax)Se2(Martin A G,Keith E,Yoshihiro H,et al.Solar cell efficiency
tables(version 41).Prog.Photovoltaics:Research and Applications.21(1):1-11,
2013)、Cu(In1-xAlx)Se2(Dhananjay,Nagaraju J,Krupanidhi S B.Structural and
optical properties of Cu(In1-xAlx)Se2thin films prepared by four-source elemental
evaporation.Solid State Commun.127(3):243-246,2003)、Cu(In1-xBx)Se2(Chen L
J,Liao J D,Chuang Y J.Self-assembled chalcopyrite ternary semiconductor
CuBSe2nanocrystals:solvothermal synthesis and characterization.CrystEngComm,
13:2909-2914,2011), Cu (In1-xCex) Se2 (Li Fu, Yongquan Guo, Shu Zheng,
Synthesis,crystal structure and optical properties of Ce doped CuInSe2powders
Prepared by mechanically alloying, 591:304 307,2014), the wherein conversion of CIGS
Efficiency reaches as high as 20.4%, but In and Ga broadly falls into dissipated metal, and usage amount is big, and reserves are few, because of
Being widely used of this Cu (InxGa1-x) Se2 solar cell is limited by bigger.
The shortcoming that the present invention is directed to above-mentioned absorbed layer material, proposes to use rare earth element yttrium (Y) doping/replacement
In prepares Cu (InxY1-x)SeyAbsorbed layer material.This material decreases the use of dissipated metal In and Ga
Amount, reduces production cost.Cu (In simultaneouslyxY1-x)SeyThe energy gap of absorbed layer material and solar energy
Optimal absorption Spectral matching degree is high, improves the photoelectric transformation efficiency of its solar cell.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of solar battery obsorbing layer material and preparation side thereof
Method.
This solar absorption layer material is the Cu (In obtained with rare earth element yttrium doping CISxY1-x)Sey,
Wherein x=0～1, y=2.0～2.5.The energy gap of this material is 1.01～1.5eV；Absorbed layer material exists
Having stronger absorbability in visible ray, absorption coefficient is more than 105cm-1, solar energy electroresponse is fast,
Be conducive to improving the photoelectric transformation efficiency of its solar cell.
The preparation method of this solar absorption layer material includes self-propagating high-temperature method and machine-alloying, Qi Zhonggao
The step of temperature self-propagating method is:
(1) according to the amount of material than Cu:In:Y:Se=1:x:(1-x): the accurate weighing of y, wherein x=0～1,
Y=2.0～2.5, then mixes in cylinder；
(2) take the compound after mixing and be placed in punching block the pressure applying 0.5-10Mpa, obtain Cu
(InxY1-x)SeyCylinder；
(3) by prepared Cu (InxY1-x)SeyCylinder is placed in autoclave, seals, and takes out true
The argon gas of charged pressure P (P=0.1～0.6MPa) after sky；
(4)Cu(InxY1-x)SeyCylinder is by being placed in parallel the discoid of its upper surface 1～2 millimeters
Tungsten filament is lighted, and stops 5s at electric current I=5A and preheats sample, be further added by I=15A by sample spot before lighting
Combustion, the solid sample obtained is Cu (InxY1-x)SeyPowder.
The step of machine-alloying is:
(1) according to the amount of material than Cu:In:Y:Se=1:x:(1-x): the accurate weighing of y, wherein x=0～1,
Y=2.0～2.5, then mixes in cylinder；
(2) being placed in planetary ball mill by alleged material, ratio of grinding media to material is 5:1～10:1, at planetary ball mill
Rotating speed is ball milling 10～120min under conditions of 500～1000r/min, and taking out the solid sample obtained is Cu
(InxY1-x)SeyPowder.
Having the beneficial effect that of the technique scheme of the present invention:
In such scheme, obtain Cu (In with rare earth element yttrium doping CISxY1-x)Sey, Cu can be reduced
(InxGa1-x)Se2In solar cell material, the usage amount of dissipated metal In and Ga, improves simultaneously
CuInSe2It is the energy gap of absorbed layer material, adds the matching of sunshine spectral response, improve
Cu(InxGa1-x)Se2The transformation efficiency of solar cell.
Accompanying drawing explanation
Fig. 1 is product CuYSe in embodiments of the invention 12XRD；
Fig. 2 is product CuYSe in embodiments of the invention 22Powder energy gap test figure.
Detailed description of the invention
For making the technical problem to be solved in the present invention, technical scheme and advantage clearer, below in conjunction with attached
Figure and specific embodiment are described in detail.
The present invention is directed to existing CIS system solar cell energy gap less, and need a large amount of dissipated metal
The problems such as In, it is provided that a kind of solar battery obsorbing layer material and preparation method thereof.
This solar absorption layer material is the Cu (In obtained with rare earth element yttrium doping CISxY1-x)Sey,
Wherein x=0～1, y=2.0～2.5.
The method preparing this material includes self-propagating high-temperature method and machine-alloying two kinds.
Embodiment 1
Self-propagating high-temperature method is used to prepare solar battery obsorbing layer material C u (InxY1-x)Sey, according to thing
The amount weighing more accurate than Cu:Y:Se=1:1:2.1 of matter, cylinder batch mixing 24h, unification weighs compound 4g
It is placed in punching block applying pressure 4MPa, prepares the cylindrical embryo of a diameter of 12mm, a height of about 10mm
Body, is placed in prepared cylinder in autoclave, seals, vacuumizes rear charged pressure P=0.1MPa
Argon gas, cylinder lighted by the discoid tungsten filament being placed in parallel its upper surface 1-2 millimeter, before lighting
Electric current I=5A stops 5s and preheats sample, is further added by I=15A and is lighted by sample, and obtain after lighting is
For CuYSe2Powder (Se in the reaction can some volatilization), its XRD is as shown in Figure 1.
Embodiment 2
Machine-alloying is used to prepare solar battery obsorbing layer material C u (InxY1-x)Sey, according to material
Amount weighing more accurate than Cu:Y:Se=1:1:2, cylinder batch mixing 24h, unified weigh compound 4g, ball material
Ratio is 6:1, is placed in planetary ball mill, and planetary ball mill rotating speed is 800r/min, and Ball-milling Time is 60min,
Prepare CuYSe2Powder, records its energy gap as shown in Figure 2.Figure it is seen that the CYS recorded
Energy gap be 1.49eV with solar cell preferable absorbed layer energy gap be 1.49eV closely.
The above is the preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, on the premise of without departing from principle of the present invention, it is also possible to make some improvements and modifications,
These improvements and modifications also should be regarded as protection scope of the present invention.
Claims (6)
1. a solar battery obsorbing layer material, it is characterised in that: this material is for adulterating CIS with rare earth element yttrium
Cu (the In obtainedxY1-x)Sey, wherein x=0～1, y=2.0～2.5.
A kind of solar battery obsorbing layer material the most according to claim 1, it is characterised in that: the taboo of this material
Bandwidth is 1.01～1.5eV；The absorption coefficient of visible ray is more than 105cm-1。
A kind of solar battery obsorbing layer material the most according to claim 1, it is characterised in that: the system of this material
Preparation Method includes self-propagating high-temperature method and machine-alloying.
The preparation method of a kind of solar battery obsorbing layer material the most according to claim 3, it is characterised in that:
The step of described self-propagating high-temperature method is:
(1) according to the amount of material than Cu:In:Y:Se=1:x:(1-x): the accurate weighing of y, wherein x=0～1, y=
2.0～2.5, then mix in cylinder；
(2) take the compound after mixing and be placed in punching block the pressure applying 0.5-10Mpa, obtain Cu (InxY1-x)SeyCircle
Cylinder；
(3) by prepared Cu (InxY1-x)SeyCylinder is placed in autoclave, seals, vacuumizes rear charged pressure P
The argon gas of=0.1～0.6MPa；
(4)Cu(InxY1-x)SeyCylinder is lighted by the discoid tungsten filament being placed in parallel its upper surface 1～2 millimeters, obtains
Solid sample be Cu (InxY1-x)SeyPowder.
A kind of preparation method preparing solar battery obsorbing layer material, it is characterised in that:
When using self-propagating high-temperature method, discoid tungsten filament stops 5s at electric current I=5A before lighting and preheats sample, then increases
It is added to I=15A lighted by sample.
The preparation method of a kind of solar battery obsorbing layer material the most according to claim 3, it is characterised in that:
The step of described machine-alloying is:
(1) according to the amount of material than Cu:In:Y:Se=1:x:(1-x): the accurate weighing of y, wherein x=0～1, y=2.0～
2.5, then mix in cylinder；
(2) being placed in planetary ball mill by alleged material, ratio of grinding media to material is 5:1～10:1, and celestial body mill speed of being expert at is
Ball milling 10～120min under conditions of 500～1000r/min, taking out the solid sample obtained is Cu (InxY1-x)Sey
Powder.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728461A (en) * | 2009-11-06 | 2010-06-09 | 清华大学 | Method for preparing absorbing layer of thin film solar cell |
| CN102983222A (en) * | 2012-12-06 | 2013-03-20 | 许昌天地和光能源有限公司 | Preparation method for absorption layer with gradient band gap distribution |
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| WO2009013285A1 (en) * | 2007-07-25 | 2009-01-29 | Polymers Crc Ltd. | Solar cell and method for preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101728461A (en) * | 2009-11-06 | 2010-06-09 | 清华大学 | Method for preparing absorbing layer of thin film solar cell |
| CN102983222A (en) * | 2012-12-06 | 2013-03-20 | 许昌天地和光能源有限公司 | Preparation method for absorption layer with gradient band gap distribution |
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