CN107381623B - A kind of intermediate carrying semiconductor material and its preparation method and application - Google Patents
A kind of intermediate carrying semiconductor material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of intermediate carrying semiconductor material and its preparation method and application, the intermediate carrying semiconductor material is to be located atP2/cThe monocline of space group, chemical formula K2Cu2GeS4.Semiconductor material K provided by the invention2Cu2GeS4Band gap be 2.3 eV, the best bandgap range that solar spectrum absorbs is 0.8-1.8 eV, and in K2Cu2GeS4Interband introduce an Intermediate Gray, edge energy between Intermediate Gray and valence band is 1.3 eV, just in sunlight optimal absorption spectral region.
Description
Technical field
The present invention relates to a kind of Intermediate Gray compounds and its preparation method and application, belong to field of material preparation.
Background technique
Environmental pollution and energy crisis are two hang-ups of facing mankind, and solar energy because its green, rich reserves, can be again
The features such as raw is considered as the most promising energy.Solar cell be the most effective way that converts solar energy into electrical energy it
One.During the utilization of solar energy, the selection and utilization of material are most important.1978 are so far, solar cell material after
Multiple innovation.From the single crystal silicon solar cell of the first generation to II-VI race's semiconductor film solar cell, then arrive the amount of the third generation
The novel solar cells such as sub- point, organic polymer, it can be seen that the innovation of material is the fundamental driving force of Solar use.
Mainly there are two aspects to restrict for the development of solar cell material, first is that the production cost of solar cell, second is that the sun
The efficiency of battery.1961, Shockky and Queisser were absorbed according to detailed balancing principle and single threshold, were calculated ideal single
The limiting efficiency of connection solar cell is 31%, and the limiting efficiency is 40.7% under full optically focused, and here it is Shockley-Queisser
The limit.In order to break through the limitation of this efficiency, 1997, Luque and Martin proposed Intermediate Gray according to detailed balance theory
The physical model of battery, be calculated it is non-concentrating under the conditions of, Intermediate Gray solar cell peak efficiency is 46.77%, and optically focused item
Under part, Intermediate Gray solar cell peak efficiency can reach 63.2%, and the limiting efficiency for solar cell of connecting with common three knot is suitable.
People are the study found that first generation single crystal silicon solar cell and second generation thin film solar cell material are mostly single band
Gap.For single tape gap material, energy cannot be absorbed lower than the photon of band gap, thus cannot by electronics from valence to
Conduction band, this is one of the main reason for causing efficiency of solar cell not high.
The research of intermediate zone material at present focuses primarily upon theoretical side, and the development of Intermediate Gray solar cell is also at primary
In the stage, problems are also faced with, the scarcity of intermediate zone material is one of the main reasons.Therefore, it designs and seeks novel centre
Carrying material has important research significance.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of intermediate carrying semiconductor material and preparation method thereof and answering
With.
On the one hand, the present invention provides a kind of intermediate carrying semiconductor material, the intermediate carrying semiconductor material is to be located at P2/
The monocline of c space group, chemical formula K2Cu2GeS4。
Semiconductor material K provided by the invention2Cu2GeS4Band gap be 2.3eV, solar spectrum absorb best band gap model
It encloses for 0.8-1.8eV, and in K2Cu2GeS4Interband introduce an Intermediate Gray, edge energy between Intermediate Gray and valence band is 1.3
EV, just in sunlight optimal absorption spectral region.The presence of Intermediate Gray, so that original unabsorbable lower energy photon energy
Enough to be absorbed that valence-band electrons is made to transit to Intermediate Gray by valence-band electrons, then it continues to absorb another lower energy photon, makes valence
Having electronic transits to conduction band from Intermediate Gray, and the photon that energy is higher than band gap can be directly absorbed, and make electronics from valence band transition
To conduction band, to realize Multiphoton Absorbtion.The presence of Intermediate Gray can effectively widen the absorption region of sunlight, improve the sun
It can utilization efficiency.
On the other hand, the present invention also provides a kind of preparation methods of above-mentioned intermediate carrying semiconductor material, comprising:
Ge source, copper source, sulphur source and potassium resource are mixed, mixture is obtained；
Gained mixture is reacted 3~7 days, then cleaned at 200~240 DEG C, obtains the Intermediate Gray semiconductor material
Material.
Preferably, after mixing by ge source, copper source and sulphur source, adding potassium resource, mixture is obtained.Potassium hydroxide is last
Add, former three needs to be uniformly mixed, and is easy to product uniformity；Potassium hydroxide is hygroscopic, and the presence of water can be such that K2Cu2GeS4 becomes
Matter in addition, potassium hydroxide can dissolve during the reaction, therefore does not need to be uniformly mixed with former three.
Preferably, in Germanium in the ge source, copper in copper source, sulphur source in element sulphur and potassium resource potassium element mole
Than for 1:1:(20~27): (35~55).
Preferably, the ge source is germanium simple substance, GeS2At least one of.
Preferably, copper source is copper simple substance and Cu2At least one of S.
Preferably, the sulphur source is one of thiocarbamide and S simple substance, preferably thiocarbamide.Wherein it is added thiocarbamide in raw material, one
For aspect thiocarbamide as sulphur source, on the one hand melting thiocarbamide can be used as the cosolvent of reaction.Thiocarbamide is helped as reaction simultaneously as sulphur source
Solvent.The fusing point of thiocarbamide be 180 DEG C, 200 DEG C of reactions that will decompose provide S, and under the conditions of 200 DEG C, thiocarbamide and
KOH can occur to react as follows: 2SC (NH2)2+2KOH→[H2N+=C (NH2)2]SCN-+K2S+2H2O.Under the conditions of the temperature, thiocarbamide
The environment of alkalinity is provided to react, facilitates sulfide and synthesizes more.
Preferably, the potassium resource is KOH and K2CO3At least one of, preferably KOH or K2CO3。
Preferably, the partial size of the ge source is 100 nanometers~10 microns, the partial size of copper source is 100 nanometers~5 micro-
Rice.
In another aspect, the present invention also provides a kind of above-mentioned intermediate carrying semiconductor materials to prepare Intermediate Gray solar battery
In application.
The method of the invention is easy to operate, prepared noval chemical compound K2Cu2GeS4It is a kind of typical semiconductor material
Material.By first-principles calculations, which is a kind of semiconductor material with Intermediate Gray, has and applies in the Intermediate Gray sun
The prospect of battery.
Detailed description of the invention
Fig. 1 is the crystal morphology figure (SEM) of 1 gained sample of the embodiment of the present invention；
Fig. 2 is elemental analysis (EDX) figure of 1 gained sample of the embodiment of the present invention；
Fig. 3 is the powder xrd pattern of 1 gained sample of the embodiment of the present invention；
Fig. 4 is the crystal structure figure of 1 gained sample of the embodiment of the present invention, wherein (a) figure is ideal anti-lead oxide structure
Cu3S4Layer, (b) figure are the [Cu of the anti-lead oxide structure of deformation2GeS4]2-Layer, (c) figure are K2Cu2GeS4Crystal structure show
It is intended to, (d) figure is [CuS4]7-、[GeS4]4-Tetrahedron and [KS8]15-Geometrical relationship schematic diagram between cube；
Fig. 5 is the ultraviolet-visible absorption spectroscopy figure of 1 gained sample of the embodiment of the present invention, and illustration is (α hv)1/2With energy
Relational graph；
Fig. 6 is the electronic band structure and density of states figure of 1 gained sample of the embodiment of the present invention, wherein (a) is gained sample
Band structure figure is (b) the total density of states figure of sample, and (c) and (d) is gained sample part density of states figure；
Fig. 7 is the powder SEM figure of 2 gained sample of the embodiment of the present invention；
Fig. 8 is the powder EDS figure of 2 gained sample of the embodiment of the present invention；
Fig. 9 is the powder xrd pattern of 3 gained sample of the embodiment of the present invention；
Figure 10 is the powder xrd pattern of 4 gained sample of the embodiment of the present invention；
Figure 11 is the powder xrd pattern of 5 gained sample of the embodiment of the present invention；
Figure 12 is the SEM figure of 6 gained sample of the embodiment of the present invention；
Figure 13 is the EDX figure of 6 gained sample of the embodiment of the present invention；
Figure 14 is the SEM figure of 7 gained sample of the embodiment of the present invention；
Figure 15 is the powder xrd pattern of 7 gained sample of the embodiment of the present invention；
Figure 16 is the comparison diagram of the XRD of the gained sample of the embodiment of the present invention 1 and 2；
Figure 17 is the comparison diagram of the SEM of the gained sample of the embodiment of the present invention 6 and 7.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
Intermediate Gray semiconductor provided by the invention is the monocline positioned at P2/c space group, and structural formula is
K2Cu2GeS4。
The present invention mixes the raw material of appropriate ratio under the environment of alkalinity, is finally prepared by flux method
K2Cu2GeS4.The material is the monocline new compound positioned at P2/c space group.The noval chemical compound that the method is prepared, which has, answers
Prospect used in Intermediate Gray solar cell field.Illustrate to following exemplary the system of intermediate carrying semiconductor material provided by the invention
Preparation Method.
Ge source, copper source, sulphur source and potassium resource are mixed, mixture is obtained.Specifically, by raw material ge source, copper source, sulphur
Source and potassium resource are mixed in a certain ratio, and grinding uniformly, obtains mixture.Germanium in the ge source, copper, sulphur source in copper source
The molar ratio of potassium element can be 1:1:(20~27 in middle element sulphur and potassium resource): (35~55), preferably 1:1:20:40.It is described
Ge source can be germanium simple substance and GeS2At least one of.Copper source can be copper simple substance and Cu2At least one of S.The sulphur source
It can be one of thiocarbamide and S simple substance, preferably thiocarbamide.The potassium resource can be KOH and K2CO3At least one of, preferably
KOH or K2CO3.In the present invention, the reaction environment of the alkalinity is by potassium resource (for example, potassium hydroxide, K2CO3Deng) provide.In addition,
Potassium resource is more preferably KOH, and KOH is alternatively arranged as mineralizer in addition to providing the reaction environment of alkalinity to improve product crystallinity.
As an example, by raw material germanium (Ge) simple substance, copper (Cu) simple substance, thiocarbamide (SC (NH2)2) be mixed in a certain ratio,
Mixture is uniformly mixed in mortar, potassium hydroxide (KOH) is added and continues to grind.The purity of selected Ge powder and Cu powder
Respectively 99.99%, the purity of other raw materials is 99.999%.GeS can be used2Substitute Ge simple substance, with etc. potassium amount of substance
K2CO3Replace KOH.
In the present invention, the partial size of the ge source can be 100 nanometers~10 microns.The partial size of copper source can be 100 nanometers
~5 microns.The sulphur source is graininess, and partial size can be 5~80 microns.The potassium resource can be graininess or sheet.In this hair
In a bright embodiment, the reaction raw materials group is combined into Ge simple substance (400 mesh), Cu simple substance (200 mesh), thiocarbamide (particle),
KOH (sheet).
Mixture is reacted 3~7 days, then cleaned at 200~240 DEG C, obtains the intermediate carrying semiconductor material.Make
For an example, mixture is put into the reaction kettle that 50mL polytetrafluoroethylene (PTFE) is liner, reaction kettle is then put into baking oven
It reacts 3-7 days, then takes out sample in the middle, clean repeatedly with distilled water, collecting underlying crystalline can be obtained Intermediate Gray
Compound (intermediate carrying semiconductor material).Wherein, the reaction temperature is within the scope of 220 ± 20 DEG C, and the reaction time is in 3-7
It.
In one embodiment of the invention, according to the yield of the product, if being 1~1.2g, when ingredient
Raw material Ge powder (0.363g), Cu powder (0.318g), thiocarbamide (7.6g), potassium hydroxide (11.22g) usage ratio are 1:1:20:
40.In one embodiment of the invention, the amount ranges of the thiocarbamide can be 7.6-10g.The Ge simple substance can be replaced
For the GeS of the amount of equal substances2.Wherein, the amount of added potassium hydroxide can be within the scope of 10~15g.The KOH could alternatively be
The K of the amount of equal potassium substance2CO3。
In one embodiment of the invention, the volume 50mL using experimental provision.Or the reaction for 25mL
Liner, still, the amount of corresponding reactant halve.
In the present invention, the preparation method of the intermediate carrying semiconductor material (intermediate zone material) is applicable to K2Cu2GeS4
The preparation of compound.The method of the present invention preparation is simple, and prepared compound has Intermediate Gray, have apply Intermediate Gray too
The prospect in positive electricity pond.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1:
The thiocarbamide for weighing the Ge powder of 0.363g, the Cu powder of 0.318g and 7.6g, which is put into mortar, to be ground uniformly, and 15g is added
KOH continue to grind, then mixture is put into the polytetrafluoroethyllining lining of 50mL, then polytetrafluoroethyllining lining is put
Enter in reaction kettle steel shell, keeps the temperature 3 days in 220 DEG C of constant temperature blast drying ovens.After being naturally cooling to room temperature, after taking out reaction
Product, in deionized water ultrasound 10 minutes, outwell upper layer suspension, take bottom sediment crystal, clean repeatedly several
It is secondary to obtain orange K2Cu2GeS4Compound is placed in the glove box full of argon gas saves later by compound.
Embodiment 2:
The thiocarbamide for weighing the Ge powder of 0.363g, the Cu powder of 0.318g and 7.6g, which is put into mortar, to be ground uniformly, and 10g is added
KOH continue to grind, then mixture is put into the polytetrafluoroethyllining lining of 50mL, then polytetrafluoroethyllining lining is put
Enter in reaction kettle steel shell, keeps the temperature 3 days in 220 DEG C of constant temperature blast drying ovens.After being naturally cooling to room temperature, after taking out reaction
Product, in deionized water ultrasound 10 minutes, outwell upper layer suspension, take bottom sediment crystal, clean repeatedly several
It is secondary to obtain orange K2Cu2GeS4Compound is placed in the glove box full of argon gas saves later by compound.
Embodiment 3:
The thiocarbamide for weighing the Ge powder of 0.363g, the Cu powder of 0.318g and 7.6g, which is put into mortar, to be ground uniformly, and 10g is added
KOH continue to grind, then mixture is put into the polytetrafluoroethyllining lining of 50mL, then polytetrafluoroethyllining lining is put into
In reaction kettle steel shell, 3 days are kept the temperature in 200 DEG C of constant temperature blast drying ovens.After being naturally cooling to room temperature, after taking out reaction
Product, ultrasound 10 minutes, outwell upper layer suspension, take bottom sediment crystal, clean repeatedly several times in deionized water
It can obtain orange K2Cu2GeS4Compound is placed in the glove box full of argon gas saves later by compound.
Embodiment 4:
The thiocarbamide for weighing the Ge powder of 0.363g, the Cu powder of 0.318g and 7.6g, which is put into mortar, to be ground uniformly, and 10g is added
KOH continue to grind, then mixture is put into the polytetrafluoroethyllining lining of 50mL, then polytetrafluoroethyllining lining is put
Enter in reaction kettle steel shell, keeps the temperature 7 days in 220 DEG C of constant temperature blast drying ovens.After being naturally cooling to room temperature, after taking out reaction
Product, in deionized water ultrasound 10 minutes, outwell upper layer suspension, take bottom sediment crystal, clean repeatedly several
It is secondary to obtain orange K2Cu2GeS4Compound is placed in the glove box full of argon gas saves later by compound.
Embodiment 5:
Weigh the Ge powder of 0.363g, the Cu of 0.398g2The thiocarbamide of S powder and 7.6g are put into mortar and grind uniformly, add
The KOH of 10g continues to grind, and then mixture is put into the polytetrafluoroethyllining lining of 50mL, then polytetrafluoroethyllining lining
It is put into reaction kettle steel shell, keeps the temperature 3 days in 220 DEG C of constant temperature blast drying ovens.After being naturally cooling to room temperature, reaction is taken out
Product afterwards, ultrasound 10 minutes, outwell upper layer suspension, take bottom sediment crystal in deionized water, if cleaning repeatedly
It can obtain orange K dry time2Cu2GeS4Compound is placed in the glove box full of argon gas saves later by compound.
Embodiment 6:
Weigh the GeS of 0.683g2, the Cu powder of 0.318g and the thiocarbamide of 7.6g be put into mortar and grind uniformly, add 10g
KOH continue to grind, then mixture is put into the polytetrafluoroethyllining lining of 50mL, then polytetrafluoroethyllining lining is put
Enter in reaction kettle steel shell, keeps the temperature 3 days in 220 DEG C of constant temperature blast drying ovens.After being naturally cooling to room temperature, after taking out reaction
Product, in deionized water ultrasound 10 minutes, outwell upper layer suspension, take bottom sediment crystal, clean repeatedly several
It is secondary to obtain orange K2Cu2GeS4Compound is placed in the glove box full of argon gas saves later by compound.
Embodiment 7:
Weigh the GeS of 0.683g2, the Cu powder of 0.318g and the thiocarbamide of 7.6g be put into mortar and grind uniformly, add
12.3g K2CO3Continue to grind, then mixture is put into the polytetrafluoroethyllining lining of 50mL, then polytetrafluoroethylene (PTFE)
Liner is put into reaction kettle steel shell, keeps the temperature 3 days in 220 DEG C of constant temperature blast drying ovens.After being naturally cooling to room temperature, take out
Product after reaction, ultrasound 10 minutes, outwell upper layer suspension, take bottom sediment crystal, repeatedly clearly in deionized water
Orange K can be obtained several times by washing2Cu2GeS4Compound is placed in the glove box full of argon gas saves later by compound.
Table 1 is K prepared by 1-7 of the embodiment of the present invention2Cu2GeS4Compound is raw materials used and preparation parameter
Sample characterization
1. the pattern and material phase analysis of powder
Morphology characterization is carried out by SEM to the resulting crystal of the present invention.EDX can carry out qualitative analysis to its ingredient.To this
It is tested after the grinding of invention gained sample, sample preparation in Bruker D8Focus X-ray diffractometer.Diffraction conditions are copper target, are swept
Retouching voltage is 40kV, and electric current 40mA, scanning angle range is 10~60 °, and scanning speed is 6 °/min；
2. the absorption spectrum of powder
Powder sample obtained by the present invention is fully ground, after sample preparation Hitachi UV-4100 spectrophotometer into
Row test.The wave-length coverage of test is 1000-400nm.Test speed is 120nm/min；
3. the structure elucidation of single crystal samples
The resulting crystal prototype of the present invention is selected, selects the single crystal samples of good crystallinity in Bruker D8Quest
Single crystal X-ray diffraction carries out crystallographic data collection, and is measured to the crystal structure of sample, then passes through Bruker
APEX3 program carries out structure elucidation and data refine.
Fig. 1 is the crystal morphology figure (SEM) of 1 gained sample of the embodiment of the present invention, as can be known from Fig. 1 K2Cu2GeS4For bulk
Crystal；
Fig. 2 is elemental analysis (EDX) figure of 1 gained sample of the embodiment of the present invention, as can be known from Fig. 2 K2Cu2GeS4Crystal contains
There are tetra- kinds of elements of K, Cu, Ge and S；
Fig. 3 is the powder xrd pattern of 1 gained sample of the embodiment of the present invention, the crystal that experiment case study 1 obtains as can be known from Fig. 3
Sample has high purity and good crystallinity；
Fig. 4 is the crystal structure figure of 1 gained sample of the embodiment of the present invention, wherein (a) figure is ideal anti-lead oxide structure
Cu3S4Layer, (b) figure are the [Cu of the anti-lead oxide structure of deformation2GeS4]2-Layer, (c) figure are K2Cu2GeS4Crystal structure show
It is intended to, (d) figure is [CuS4]7-、[GeS4]4-Tetrahedron and [KS8]15-Geometrical relationship schematic diagram between cube, from Fig. 4
Know K2Cu2GeS4It is a kind of compound with layer structure；
Fig. 5 is the ultraviolet-visible absorption spectroscopy figure of 1 gained sample of the embodiment of the present invention, and illustration is (α hv)1/2With energy
Relational graph, as can be known from Fig. 5 K2Cu2GeS4Optical band gap be 2.3eV；
Fig. 6 is the electronic band structure and density of states figure of 1 gained sample of the embodiment of the present invention, wherein (a) is gained sample
Band structure figure is (b) the total density of states figure of sample, and (c) and (d) is gained sample part density of states figure, as can be known from Fig. 6
K2Cu2GeS4It is a kind of semiconductor material with Intermediate Gray, in-between band is mainly contributed by S-3p and Ge-4s track；
Fig. 7 is the SEM figure of 2 gained sample of the embodiment of the present invention, as can be known from Fig. 7 K2Cu2GeS4For bulk crystals；
Fig. 8 is the EDS figure of 2 gained sample of the embodiment of the present invention, as can be known from Fig. 8 K2Cu2GeS4Crystal contains K, Cu, Ge
With tetra- kinds of elements of S；
Fig. 9 is the XRD diagram of 3 gained sample of the embodiment of the present invention, the crystal prototype that experiment case study 3 obtains as can be known from Fig. 9
With high purity and good crystallinity；
Figure 10 is the powder xrd pattern of 4 gained sample of the embodiment of the present invention, the crystalline substance that experiment case study 4 obtains as can be known from Fig. 10
Body sample has high purity and good crystallinity.
Figure 11 is the powder xrd pattern of 5 gained sample of the embodiment of the present invention, the crystalline substance that experiment case study 5 obtains as can be known from Fig. 11
Body sample has high purity and good crystallinity；
Figure 12 is the powder SEM figure of 6 gained sample of the embodiment of the present invention, as can be known from Fig. 12 K2Cu2GeS4It is blocky brilliant
Body；
Figure 13 is the EDS figure of 6 gained sample of the embodiment of the present invention, as can be known from Fig. 13 K2Cu2GeS4Crystal contain K, Cu,
Tetra- kinds of elements of Ge and S；
Figure 14 is the powder SEM figure of 7 gained sample of the embodiment of the present invention, as can be known from Fig. 14 K2Cu2GeS4It is blocky brilliant
Body；
Figure 15 is the powder xrd pattern of 7 gained sample of the embodiment of the present invention, the crystalline substance that experiment case study 7 obtains as can be known from Fig. 15
Body sample has high purity and good crystallinity；
Figure 16 is the comparison diagram of the XRD of the gained sample of the embodiment of the present invention 1 and 2, and product can be improved in KOH as can be known from Fig. 16
Crystallinity；
Figure 17 is the comparison diagram of the SEM of the gained sample of the embodiment of the present invention 6 and 7, wherein (a) is 6 gained sample of embodiment
SEM figure, (b) for 7 gained sample of embodiment SEM scheme, product crystallinity can be improved in KOH as can be known from Fig. 17.
Table 2 is K prepared by embodiment 12Cu2GeS4EDS data:
Table 3 is K prepared by the embodiment of the present invention 12Cu2GeS4Crystal data and refine data:
Table 4 is K prepared by embodiment 62Cu2GeS4EDS data:
Claims (11)
1. a kind of intermediate carrying semiconductor material, which is characterized in that the intermediate carrying semiconductor material is to be located atP2/cSpace group
Monocline, the intermediate carrying semiconductor material have the semiconductor material of layer structure and Intermediate Gray, and chemical formula is
K2Cu2GeS4。
2. a kind of preparation method of intermediate carrying semiconductor material as described in claim 1 characterized by comprising
Ge source, copper source, sulphur source and potassium resource are mixed, mixture is obtained, Germanium in the ge source, copper in copper source,
The molar ratio of potassium element is 1:1:(20~27 in element sulphur and potassium resource in sulphur source): (35~55)；
Gained mixture is reacted 3~7 days, then cleaned at 200~240 DEG C, obtains the intermediate carrying semiconductor material.
3. preparation method according to claim 2, which is characterized in that after mixing by ge source, copper source and sulphur source, then plus
Enter potassium resource, obtains mixture.
4. preparation method according to claim 2, which is characterized in that the ge source is germanium simple substance and GeS2In at least one
Kind.
5. preparation method according to claim 2, which is characterized in that copper source is copper simple substance and Cu2At least one in S
Kind.
6. preparation method according to claim 2, which is characterized in that the sulphur source is one in thiocarbamide and simple substance sulphur powder
Kind.
7. preparation method according to claim 6, which is characterized in that the sulphur source is thiocarbamide.
8. preparation method according to claim 2, which is characterized in that the potassium resource is KOH and K2CO3At least one of.
9. preparation method according to claim 8, which is characterized in that the potassium resource is KOH or K2CO3。
10. the preparation method according to any one of claim 2-9, which is characterized in that the partial size of the ge source is received for 100
Rice~10 microns, the partial size of copper source are 100 nanometers~5 microns.
11. a kind of carrying semiconductor material intermediate as described in the appended claim 1 is preparing the application in Intermediate Gray solar battery.
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