CN101519307A - Method for preparing CIS powder and target thereof - Google Patents

Method for preparing CIS powder and target thereof Download PDF

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Publication number
CN101519307A
CN101519307A CN200810007546A CN200810007546A CN101519307A CN 101519307 A CN101519307 A CN 101519307A CN 200810007546 A CN200810007546 A CN 200810007546A CN 200810007546 A CN200810007546 A CN 200810007546A CN 101519307 A CN101519307 A CN 101519307A
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initiator
powder
cis
cucl
making method
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傅耀贤
黄文启
周邦彦
林世仁
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Nanowin Tech Co Ltd
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Nanowin Tech Co Ltd
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Abstract

A method for preparing CIS powder comprises the following steps: a Cu-containing initiator, an M1-containing initiator, an M2-containing initiator and a chimera solvent are mixed in a reaction groove containing inert gas so as to lead the chimera solvent to extract the cations and anions of the initiators and form an homogeneous-phase parent compound containing Cu, M1 and M2, wherein the homogeneous-phase parent compound is refluxed and further reacted to form the powder containing chalcopyrite crystal phase; M1 is selected from the following elements: In, Ga or the combination thereof; and M2 is selected from the following elements: Se, S or the combination thereof. In addition, the invention also provides a method for preparing the CIS target which is the CIS powder prepared by the above method.

Description

CIS is the making method of powder and the making method of target thereof
Technical field
The present invention relates to a kind of making method of powder, be meant that especially a kind of CIS (copper indiumchalcogenides) is the making method of powder and the making method of target (target) thereof.
Background technology
For solving problems such as human energy dilemma that is faced because of excessive exploitation in recent decades and environmental pollution, the exploitation of solar cell (solar cell) sternly so becomes the main research topic of problem such as solution energy dilemma.
With two copper indium diselenide (CuInSe 2) in the solar cell of the ternary compound CIS system of deriving out, its p N-type semiconductorN absorption layer common CIS based material CuInSe is then arranged 2, Cu (In xGa 1-x) (Se yS 2-y), Cu (In xAl 1-x) (Se yS 2-y) etc.Because this type of CIS based material has characteristics such as high photoelectric efficiency (efficiency) and low material cost, therefore, is also had an optimistic view of by the person of ordinary skill in the field.
People such as Claire J.Carmalt are at J.Mater.Chem., and 1998,8 (10), the making method that a kind of CIS is a powder is disclosed in the 2209-2211 article.People such as Claire J.Carmalt be mixed C uBr (0.186g, 1.30mmol), InCl 3(0.280g, 1.30mmol), Na 2Se (2.60mmol) and C 7H 8(20cm 3); In addition, heat up and reflux (reflux) after about 72 hours, reaction product is left standstill and extracts C 7H 8To stay solid-state reaction product; Wherein, CuBr can use CuCl 2(0.174g 1.30mmol) replaces.Further, solid-state reaction product is ground and carry out vacuum-drying; At last, this type of solid-state reaction product being carried out 500 ℃ of following calcinings of 24 hours (calcining) manufacture method is powder with the CIS that forms chalcopyrite crystalline phase (chalcopyrite phase).
The making methods that the people delivered such as Claire J.Camalt, not only needing to reach under 500 ℃ the CIS that 24 hours calcining just obtained the chalcopyrite crystalline phase is powder.In addition, it should be noted that when CIS be when having zink sulphide crystalline phase (sphalerite phase) in the powder, also will influence the photoelectric efficiency of material itself.Yet the X-ray diffraction of document (X-ray diffraction, be called for short XRD) can show as can be known by spectrogram thus, this method still have many these technical fields do not wish the diffracted signal peak of the zink sulphide crystalline phase seen.Therefore, the prepared CIS of this method be powder in the application of solar cell, also be restricted because of its photoelectric efficiency is not enough.
In addition, people such as By Bin Li are at Adv.Mater.1999, and 11, No.17 discloses a kind of CuInSe in the 1456-1459 article 2Nanowhisker (nanowhiskers) and the making method of nanoparticle (nanoparticles).People such as By Bin Li are mixed with CuCl in autoclave (autoclave) 22H 2O (0.221g, 1.26mmol), InCl 34H 2O (0.380g, 1.29mmol), Se (0.205g, 2.59mmol) and liquid level reach 90% aqueous diethylamide (hydrous diethylamine) of autoclave approximately, the sealing autoclave also kept 15 hours under 180 ℃ of temperature.Further, make autoclave be cooled to room temperature, the throw out in the autoclave is through filtering and utilize distilled water and ethanol to clean the several back to remove its by product.At last, reaction product is positioned under the vacuum environment that to adopt 60 ℃ temperature drying be powder to obtain CIS in 4 hours.
Though the CIS that employed solvent thermal synthesis methods of people (solvothermal synthesis) such as By Bin Li can obtain are the chalcopyrite crystalline phase is a powder; Yet, the XRD that document disclosed thus can show as can be known by spectrogram, the prepared CIS of this kind solvent thermal synthesis method be powder also have many these technical fields do not wish the diffracted signal peak (diffraction surfaces such as (103), (211), (301), (400) just) of the zink sulphide crystalline phase seen.In addition, because the more little pressure of autoclave is easy to control more, and the big more pressure of autoclave is wayward more; In addition, when implementing the solvent thermal synthesis method, be used for sealing in the autoclave of its reactant and do not dispose agitator, its collision probability that has reduced between the reactant has also relatively reduced its speed of reaction.Therefore, using the solvent thermal synthesis method is to reach the mass production that CIS is a powder.
By above stated specification as can be known, the CIS that obtains high chalcopyrite crystalline phase is the making method of powder and makes its making method reach the effect of volume production, be research and development CIS be powder association area problem to be broken through.
Summary of the invention
Brief summary of the invention
Impel compound to be the condition of crystallization phases, its main decisive is to be whether the heat energy that temperature of reaction provides is enough to make that each atom in the compound is occupied its crystallographic site (lattice site) in crystal.
What deserves to be mentioned is, contain the solvent that negatively charged ion and cationic ionic compound are arranged in pairs or groups and used when multiple, be belong to can in this type of ionic compound, extract fully negatively charged ion and metallic cation with form respectively one be homogeneous phase (homogeneous phase) contain mosaic (chelate) solvent of this type of ionic parent (precursor) time; So, contain this type of sun/anionic parent in solvent through after the backflow of a scheduled time and reaction form in the process of crystalline phase with particular chemical dosage ratio, its required reaction energy just can relatively descend.
Therefore, the present invention mainly is that the negatively charged ion and the positively charged ion that utilize the solvent with mosaic to extract in the initiator are homogeneous and contain this anionoid and cationic parent to form one, treat this parent just can be under the situation that reaction can descend after one scheduled time of mosaic solvent internal reflux (under the non high temperature high pressure) react formation and have the crystalline phase of predetermined chemical dosage ratio.
Goal of the invention
The object of the present invention is to provide a kind of CIS is the making method of powder.
Another object of the present invention is to provide a kind of making method of CIS series target material.
Therefore, CIS of the present invention is the making method of powder, comprising: the initiator, a kind of M of containing that mix a kind of Cu of containing in a reactive tank that contains rare gas element 1Initiator, a kind of M that contains 2Initiator and a kind of mosaic solvent so that this mosaic solvent extracts the positively charged ion and the negatively charged ion of described initiator in this reactive tank, and form one and be homogeneous and contain Cu, M 1With M 2Parent.
Wherein, this be the homogeneous parent after refluxing further reaction form the powder that contains the chalcopyrite crystalline phase, M 1Be to be selected from following element: In, Ga, or its combination, M 2Be to be selected from following element: Se, S, or its combination.
In addition, the making method of CIS series target material of the present invention comprises following steps:
(a) inserting the prepared CIS of above-mentioned making method in an intravital mould in chamber is powder;
(b) this cavity is reduced pressure to form a purification cavity;
(c) the intravital powder in this chamber is heated up reach a preset temperature and scheduled time of constant temperature;
(d) to this intravital powder in purification chamber boost reach a predetermined pressure and constant voltage should the scheduled time, causing this CIS is that powder is by obtaining the energy of powder densification (densification) by this preset temperature and predetermined pressure; And
(e) remove this predetermined pressure and in this purification cavity, introduce rare gas element to cool off this purification cavity.
Beneficial effect of the present invention is, the CIS that does not need just can to obtain high chalcopyrite crystalline phase under the manufacturing conditions of High Temperature High Pressure is a powder, and makes its making method reach the effect of volume production; In addition, be the making method of powder and made the CIS series target material by the CIS of mass production.
Description of drawings
The present invention is described in detail below in conjunction with drawings and Examples:
Fig. 1 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 1 of the making method of powder.
Fig. 2 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 2 of the making method of powder.
Fig. 3 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 3 of the making method of powder.
Fig. 4 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 4 of the making method of powder.
Fig. 5 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 5 of the making method of powder.
Fig. 6 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 6 of the making method of powder.
Fig. 7 is an XRD energy spectrogram, illustrates that by this embodiment of the invention 6 prepared CIS be the crystalline phase of the made target of powder.
Fig. 8 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 7 of the making method of powder.
Fig. 9 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 8 of the making method of powder.
Figure 10 is that XRD can spectrogram, illustrates that CIS of the present invention is the crystalline phase of an embodiment 9 of the making method of powder.
Figure 11 is an XRD energy spectrogram, and the crystalline phase of a comparative example 1 that is used for comparing with various embodiments of the present invention is described.
Figure 12 is an XRD energy spectrogram, and the crystalline phase of a comparative example 2 that is used for comparing with various embodiments of the present invention is described.
Embodiment
Detailed description of the invention
Aforementioned and other technology contents, characteristics and beneficial effect about the present invention in the detailed description below in conjunction with a preferred embodiment of accompanying drawing, nine embodiment and two comparative examples, can clearly present.
CIS of the present invention is a preferred embodiment of the making method of powder, comprising: the initiator, a kind of M of containing that mix a kind of Cu of containing in a reactive tank that contains rare gas element 1Initiator, a kind of M that contains 2Initiator and a kind of mosaic solvent so that this mosaic solvent extracts the positively charged ion and the negatively charged ion of described initiator in this reactive tank, and form one and be homogeneous and contain Cu, M 1With M 2Parent.
Wherein, this be the homogeneous parent be middle stirring and after refluxing further reaction form the powder that contains the chalcopyrite crystalline phase, M 1Be to be selected from following element: In, Ga, or its combination, M 2Be to be selected from following element: Se, S, or its combination.
Be applicable to that mosaic solvent of the present invention is to be selected from following at least a solvent: quadrol (ethylenediamine, abbreviation ED), dimethyl formamide (dimethyl formamide, abbreviation DMF), N,N-DIMETHYLACETAMIDE (dimethyl acetamide), dimethyl sulfoxide (DMSO) (dimethylsulfoxide, abbreviation DMSO), N-crassitude (N-methylpyrrolidone, be called for short NMP), or pyridine (pyridine); The initiator that is applicable to the Cu of containing of the present invention is to be selected from following at least a material: CuCl, CuCl 22H 2O, or CuSO 4Be applicable to the M of containing of the present invention 1Initiator be to be selected from following at least a material: InCl 34H 2O, In 2O 3, In (NO 3) 3, Ga, or GaCl 3Be applicable to the M of containing of the present invention 2Initiator be to be selected from following at least a material: Se, Na 2Se, or S; And the rare gas element in this reactive tank is to be selected from following at least a rare gas element: N 2, Ar, or He.Preferably, the usage quantity of this mosaic solvent be the liquid level of this reactive tank 50%～90% between; Reflux temperature in this reactive tank is between 90 ℃～300 ℃; The return time of the parent in this reactive tank is between 4 hours～48 hours.More preferably, the reflux temperature in this reactive tank is between 120 ℃～300 ℃; The return time of the parent in this reactive tank is between 8 hours～48 hours.
More preferably, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; And CuCl, InCl 34H 2The mole ratio of O, Ga and Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
More preferably, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2O; This contains M 2Initiator be Se; And CuCl, InCl 34H 2The mole ratio of O and Se is between 0.90:1.10:1.90～1.10:0.90:2.20.
More preferably, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be In 2O 3A kind of combination with Ga; This contains M 2Initiator be Se; And CuCl, In 2O 3, Ga and Se mole ratio be between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
More preferably, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be In (NO 3) 3A kind of combination with Ga; This contains M 2Initiator be Se; And CuCl, In (NO 3) 3, Ga and Se mole ratio be between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
More preferably, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Na 2Se; And CuCl, InCl 34H 2O, Ga and Na 2The mole ratio of Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
More preferably, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl 22H 2O; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; And CuCl 22H 2O, InCl 34H 2The mole ratio of O, Ga and Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
More preferably, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl 22H 2O; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Na 2Se; And CuCl 22H 2O, InCl 34H 2O, Ga and Na 2The mole ratio of Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
More preferably, this mosaic solvent is a quadrol; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; And CuCl, InCl 34H 2The mole ratio of O, Ga and Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
More preferably, this mosaic solvent is a quadrol; This initiator that contains Cu is CuCl 22H 2O; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; And CuCl 22H 2O, InCl 34H 2The mole ratio of O, Ga and Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
In addition, a preferred embodiment of the making method of CIS series target material of the present invention comprises following steps:
(a) in an intravital mould in chamber, (scheme not show) that inserting the prepared CIS of above-mentioned making method is powder;
(b) this cavity is reduced pressure to form a purification cavity;
(c) the intravital powder in this chamber is heated up reach a preset temperature and scheduled time of constant temperature;
(d) to this intravital powder in purification chamber boost reach a predetermined pressure and constant voltage should the scheduled time, causing this CIS is powder is obtained the powder densification by this preset temperature and predetermined pressure energy; And
(e) remove this predetermined pressure and in this purification cavity, introduce rare gas element to cool off this purification cavity.
What deserves to be mentioned is that the purpose that this step of the present invention (b) is implemented decompression mainly is to be to purify this cavity; When this purifies the pressure of cavity when excessive, will be in the process of implementing this step (c), (d) because of the excessive the present invention of generation of the intravital impurity residual quantity in this purification chamber do not wish the impurity compound seen.Therefore, preferably, the pressure of the purification cavity of this step (b) is 10 -2Torr～10 -5Between the Torr.
What deserves to be mentioned is that again the main purpose of this step of the present invention (c), (d) is to be to make that this CIS is the effect that powder produces densification.In the making method of target of the present invention, the temperature rise rate of this step (c) is the rate of pressure rise that is decided by this step (d), just, is principle with the preset temperature that reaches this step (c) simultaneously and the predetermined pressure of this step (d).Therefore, preferably, the temperature rise rate of this step (c) is between 2 ℃/min～10 ℃/min; The rate of pressure rise of this step (d) is between 1MPa/min～3MPa/min.
In addition, in the making method of target of the present invention, mainly be to make that by the energy that temperature and pressure are produced this CIS is that powder is able to by diffusion and the mechanism of sintering (sintering) to produce densification.And what deserves to be mentioned is, when preset temperature, predetermined pressure or the scheduled time of this step (c), (d) are not enough, will make that the structure of final prepared target is too loose; herein On the contrary, when the predetermined pressure of this step (d) or the scheduled time are excessive, just there is not substantial contribution for the powder densification; In addition, also will cause meaningless production cost.More be noted that herein, when the preset temperature of this step (c) is too high, will make final prepared target because of phase change (phase transition) generate the present invention do not wish the δ phase seen.Therefore, preferably, the preset temperature of this step (c) is between 500 ℃～800 ℃; The predetermined pressure of this step (d) is between 60MPa～180MPa; The scheduled time of this step (c), (d) is between 1 hour～8 hours.
And what deserves to be mentioned is that the making method of target of the present invention mainly is to make that by the energy that temperature and pressure are produced this CIS is that powder produces densification; Therefore, when this preset temperature convergence is above-mentioned define 500 ℃ times, be to supply and form the required energy of densification by improving this predetermined pressure.
Embodiment 1
At CIS of the present invention is among the embodiment 1 of making method of powder, and the rare gas element in this reactive tank is N 2This mosaic solvent is the DMF of volume 1200ml; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; Stir speed (S.S.) is 300rpm; Reflux temperature and return time are respectively 180 ℃ and 48 hours.
In addition, in this embodiment 1, the liquid level of DMF in this reactive tank reaches 60%; CuCl, InCl 34H 2The mole ratio of O, Ga and Se is 1:0.8:0.2:2; And CuCl, InCl 34H 2The consumption of O, Ga and Se is respectively 102.96g, 243.36g, 14.56g and 164.32g.By this embodiment of the invention 1 prepared CIS is that powder is that weight is that 339.77g and median size are the CuIn of 1 μ m～5 μ m 0.8Ga 0.2Se 2Powder.
See also Fig. 1, by this embodiment of the invention 1 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, and 1 of this embodiment locates to have respectively faint (400) and the zink sulphide crystalline phase diffracted signal peak of crystal faces such as (316) at about 65 ° with 71 °.Apparently, just can to make the CIS of a large amount of and highly purified chalcopyrite crystalline phase under 180 ℃ manufacture method temperature be powder in the present invention.
Embodiment 2
CIS of the present invention is that the embodiment 2 of making method of powder is roughly identical with embodiment 1, and it does not exist together and only is that this contains M 1Initiator be InCl 34H 2O; And CuCl, InCl 34H 2The mole ratio of O and Se is 1:1:2.In addition, in this embodiment 2, CuCl, InCl 34H 2The consumption of O and Se is respectively 102.96g, 304.2g and 164.32g.By embodiments of the invention 2 prepared CIS is that powder is that weight is that 349.44g and median size are the CuInSe of 1 μ m～5 μ m 2Powder.
See also Fig. 2, by this embodiment of the invention 2 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, 2 of this embodiment in about 65 °, 71 ° with 82 ° of zink sulphide crystalline phase diffracted signal peaks of locating to have respectively faint (400), (316) and crystal faces such as (424).Apparently, just can to make the CIS of a large amount of and highly purified chalcopyrite crystalline phase under 180 ℃ manufacture method temperature be powder in the present invention.
Embodiment 3
CIS of the present invention is that the embodiment 3 of making method of powder is roughly identical with embodiment 1, and it does not exist together and only is that this contains M 1Initiator be In 2O 3A kind of combination with Ga; And CuCl, In 2O 3, Ga and Se mole ratio be 1:0.8:0.2:2.In addition, in this embodiment 3, CuCl, In 2O 3, Ga and Se consumption be respectively 102.96g, 229.63g, 14.56g and 164.32g.By embodiments of the invention 3 prepared CIS is that powder is that weight is that 339.47g and median size are the CuIn of 1 μ m～5 μ m 0.8Ga 0.2Se 2Powder.
See also Fig. 3, by this embodiment of the invention 3 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, 3 of this embodiment about 65 °, 71 ° with 82 ° of zink sulphide crystalline phase diffracted signal peaks of locating to have respectively faint (400), (316) and crystal faces such as (424).Apparently, just can to make the CIS of a large amount of and highly purified chalcopyrite crystalline phase under 180 ℃ manufacture method temperature be powder in the present invention.
Embodiment 4
CIS of the present invention is that the embodiment 4 of making method of powder is roughly identical with embodiment 1, and it does not exist together and only is that this contains M 1Initiator be In (NO 3) 3A kind of combination with Ga; And CuCl, In (NO 3) 3, Ga and Se mole ratio be 1:0.8:0.2:2.In addition, in this embodiment 4, CuCl, In (NO 3) 3, Ga and Se consumption be respectively 102.96g, 249.6g, 14.56g and 164.32g.By embodiments of the invention 4 prepared CIS is that powder is that weight is that 339.77g and median size are the CuIn of 1 μ m～5 μ m 0.8Ga 0.2Se 2Powder.
See also Fig. 4, by this embodiment of the invention 4 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, 4 of this embodiment about 65 °, 71 ° with 82 ° of zink sulphide crystalline phase diffracted signal peaks of locating to have respectively faint (400), (316) and crystal faces such as (424).Apparently, just can to make the CIS of a large amount of and highly purified chalcopyrite crystalline phase under 180 ℃ manufacture method temperature be powder in the present invention.
Embodiment 5
CIS of the present invention is that the embodiment 5 of making method of powder is roughly identical with embodiment 1, and it does not exist together and only is that this contains M 2Initiator be Na 2Se; And CuCl, InCl 34H 2O, Ga and Na 2The mole ratio of Se is 0.9:0.88:0.22:2.2.In addition, in this embodiment 5, CuCl, InCl 34H 2O, Ga and Na 2The consumption of Se is respectively 92.66g, 267.70g, 16.02g and 286g.By embodiments of the invention 5 prepared CIS is that powder is that weight is that 360.54g and median size are the CuIn of 1 μ m～5 μ m 0.8Ga 0.2Se 2Powder.
See also Fig. 5, by this embodiment of the invention 5 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, and 5 of this embodiment locate to have respectively faint (400) and the zink sulphide crystalline phase diffracted signal peak of crystal faces such as (316) at about 65 ° with 71 °.Apparently, the CIS that just can make a large amount of and highly purified chalcopyrite crystalline phase under this manufacture method temperature of 180 ℃ of the present invention is a powder.
Embodiment 6
CIS of the present invention is that the embodiment 6 of making method of powder is roughly identical with embodiment 1, and it does not exist together and only is, this initiator that contains Cu is CuCl 22H 2O; And CuCl 22H 2O, InCl 34H 2The mole ratio of O, Ga and Se is 1:0.8:0.2:2.In addition, in this embodiment 6, CuCl 22H 2O, InCl 34H 2The consumption of O, Ga and Se is respectively 177.32g, 243.36g, 14.56g and 164.32g.By embodiments of the invention 6 prepared CIS is that powder is that weight is that 339.77g and median size are the CuIn of 1 μ m～5 μ m 0.8Ga 0.2Se 2Powder.
See also Fig. 6, by embodiments of the invention 6 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, and 6 of this embodiment locate to have respectively faint (400) and the zink sulphide crystalline phase diffracted signal peak of crystal faces such as (316) at about 65 ° with 71 °.Apparently, just can to make the CIS of a large amount of and highly purified chalcopyrite crystalline phase under 180 ℃ manufacture method temperature be powder in the present invention.
In addition, in the intravital mould in this chamber (figure does not show), fill 6 prepared CuIn by this embodiment 0.8Ga 0.2Se 2The about 80g of powder; Further, with the temperature rise rate of 5 ℃/min to this CuIn 0.8Ga 0.2Se 2Powder heats up and simultaneously this cavity is vacuumized; Intravital vacuum tightness reaches 2.0 * 10 when this chamber -3(last about 1 hour) during the Torr left and right sides, in this cavity, introduce Ar, and respectively with the rate of pressure rise of identical temperature rise rate and 1.7MPa/min to this CuIn 0.8Ga 0.2Se 2Powder heats up and boosts and reaches this preset temperature and predetermined pressure (lasting 1.5 hours approximately); At last, after lasting 4 hours under constant voltage and the constant temperature, remove this predetermined pressure and under the atmosphere of Ar naturally cooling to make the CIS series target material.
In this embodiment 6, the outward appearance of this CIS series target material is that diameter and thickness are distinguished the discoideus of 3 inches (in) and 3mm; This predetermined pressure and preset temperature are respectively 150MPa and 780 ℃.
See also Fig. 7, XRD by the prepared CIS series target material of the powder of this embodiment of the invention 6 can show as can be known by spectrogram, three big diffracted signal peaks of the target of this embodiment 6 are respectively (112), (204/220) and crystal faces such as (312), and obviously the target of this embodiment of the invention 6 is CIS series target materials of highly purified chalcopyrite crystalline phase.
Embodiment 7
CIS of the present invention is that the embodiment 7 of making method of powder is roughly identical with embodiment 6, and it does not exist together and only is that this contains M 2Initiator be Na 2Se; And CuCl 22H 2O, InCl 34H 2O, Ga and Na 2The mole ratio of Se is 1.1:0.72:0.18:1.9.In addition, in this embodiment 7, CuCl 22H 2O, InCl 34H 2O, Ga and Na 2The consumption of Se is respectively 195.05g, 219.02g, 13.10g and 247g.By embodiments of the invention 7 prepared CIS is that powder is that weight is that 327.22g and median size are the CuIn of 1 μ m～5 μ m 0.8Ga 0.2Se 2Powder.
See also Fig. 8, by this embodiment of the invention 7 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, and 7 of this embodiment locate to have respectively faint (400) and the zink sulphide crystalline phase diffracted signal peak of crystal faces such as (316) at about 65 ° with 71 °.Apparently, just can to make the CIS of a large amount of and highly purified chalcopyrite crystalline phase under 180 ℃ manufacture method temperature be powder in the present invention.
Embodiment 8
CIS of the present invention is that the embodiment 8 of making method of powder is roughly identical with embodiment, and it does not exist together and only is, the quadrol (ED) that this mosaic solvent is volume 1200ml.By embodiments of the invention 8 prepared CIS is that powder is that weight is that 339.77g and median size are the CuIn of 1 μ m～5 μ m 0.8Ga 0.2Se 2Powder.
See also Fig. 9, by this embodiment of the invention 8 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, 8 of this embodiment about 65 °, 71 ° with 82 ° of zink sulphide crystalline phase diffracted signal peaks of locating to have respectively faint (400), (316) and crystal faces such as (424).Apparently, just can to make the CIS of a large amount of and highly purified chalcopyrite crystalline phase under 180 ℃ manufacture method temperature be powder in the present invention.
Embodiment 9
CIS of the present invention is that the embodiment 9 of making method of powder is roughly identical with embodiment 8, and it does not exist together and only is, this initiator that contains Cu is CuCl 22H 2O; And CuCl 22H 2O, InCl 34H 2The consumption of O, Ga and Se is respectively 177.32g, 243.36g, 14.56g and 164.32g.By embodiments of the invention 9 prepared CIS is that powder is that weight is that 349.44g and median size are the CuIn of 1 μ m～5 μ m 0.8Ga 0.2Se 2Powder.
See also Figure 10, by embodiments of the invention 9 prepared CIS is that the analytical data that the XRD of powder can spectrogram shows as can be known, 9 of this embodiment about 65 °, 71 ° with 82 ° of zink sulphide crystalline phase diffracted signal peaks of locating to have respectively faint (400), (316) and crystal faces such as (424).Apparently, just can to make the CIS of a large amount of and highly purified chalcopyrite crystalline phase under 180 ℃ manufacture method temperature be powder in the present invention.
Comparative example
Be used for the comparative example 1～2 of comparing with embodiment of the present invention, roughly identical with embodiment 1, it does not exist together and only is this comparative example the 1, the 2nd, and (tetrahydrofuran, chemical formula are C to use tetrahydrofuran (THF) respectively 4H 8O is called for short THF) (chloroform, chemical formula are CHCl with chloroform 3) wait and do not have a solvent of mosaic.
See also Figure 11～12, analytical data that can spectrogram by the XRD of described comparative example shows as can be known, described comparative example because of use do not have the solvent of mosaic can't be effectively from initiator (just, CuCl, InCl 34H 2O, Ga and Se) middle its positively charged ion and the negatively charged ion of extracting; Therefore, can't direct reaction under 180 ℃ reflux temperature forming the CIS that is rich in the chalcopyrite crystalline phase is powder, and in Figure 11～12 26.6 °, 45 ° with 52.5 ° of three big diffracted signal peaks of locating to fail to show (112), (204), (220) and crystal faces such as (312).
The detailed difference of described comparative example and embodiment of the present invention put in order simply under tabulate in 1.
Table 1
Figure A200810007546D00171
Explanation by aforementioned each embodiment as can be known, the present invention is able in the process of mixing initiator and solvent because of the solvent that makes the apparatus mosaic, the positively charged ion and the negatively charged ion that extract in the initiator by the solvent that is mosaic are the homogeneous parent with formation, and under the reflux temperature condition of the boiling point that is lower than this mosaic solvent (being 180 ℃ in various embodiments of the present invention), this parent directly being reacted form the CIS that is rich in the chalcopyrite crystalline phase is powder.
In addition, CIS of the present invention is that the making method of powder is a powder because of it uses the characteristics of mosaic solvent to be made a large amount of CIS also; Therefore, by CIS of the present invention is that the prepared CIS of making method of powder is that powder more can be made the special-purpose target of sputtering system (sputtering system) by the manufacture method of powder metallurgy (powder metallurgy) further, is beneficial to the exploitation of solar cell industry.
What deserves to be mentioned is that the CIS that the present invention is generated by this embodiment 1～9 is that amount of powder reaches about 350g approximately, is the reactive tank of 2000ml though the employed reactive tank of described embodiment is laboratory tailored version and volume; Yet, when implement CIS of the present invention be powder making method (just, wet chemical synthesis method (chemical reflux synthesis method)) generate CIS when being powder employed reactive tank be when being replaced with the reactive tank of yield production type, its CIS is that the growing amount of powder just can relatively not increase; In addition, in making processes, its manufacture method easy temperature control system; In addition, that compares with the solvent thermal synthesis method is following, and the present invention also can be along with stirring action to increase its speed of reaction; Therefore, more help the exploitation of solar cell related industries.
In sum, CIS of the present invention is the making method of powder and the making method of target thereof, the CIS that does not need just can to make in large quantities highly purified chalcopyrite crystalline phase under the manufacturing conditions of High Temperature High Pressure is a powder, and be that powder more can be because of the exploitation of the making assisted solar battery related industries of target, so can reach purpose of the present invention really by the prepared CIS of the making method of this mass production.

Claims (17)

1, a kind of CIS is the making method of powder, it is characterized in that, CIS is that the making method of powder comprises:
The initiator, a kind of M of containing that in a reactive tank that contains rare gas element, mix a kind of Cu of containing 1Initiator, a kind of M that contains 2Initiator and a kind of mosaic solvent so that this mosaic solvent extracts the positively charged ion and the negatively charged ion of described initiator in this reactive tank, and form one and be homogeneous and contain Cu, M 1With M 2Parent;
Wherein, this be the homogeneous parent after refluxing further reaction form the powder that contains the chalcopyrite crystalline phase, M 1Be to be selected from following element: In, Ga, or its combination, M 2Be to be selected from following element: Se, S, or its combination.
2, CIS according to claim 1 is the making method of powder, it is characterized in that, this mosaic solvent is to be selected from following at least a solvent: quadrol, dimethyl formamide, N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N-crassitude, or pyridine; This initiator that contains Cu is to be selected from following at least a material: CuCl, CuCl 22H 2O, or CuSO 4This contains M 1Initiator be to be selected from following at least a material: InCl 34H 2O, In 2O 3, In (NO 3) 3, Ga, or GaCl 3This contains M 2Initiator be to be selected from following at least a material: Se, Na 2Se, or S.
3, CIS according to claim 2 is the making method of powder, it is characterized in that, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; And CuCl, InCl 34H 2The volumetric molar concentration of O, Ga and Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
4, CIS according to claim 2 is the making method of powder, it is characterized in that, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2O; This contains M 2Initiator be Se; And CuCl, InCl 34H 2The volumetric molar concentration of O and Se is between 0.90:1.10:1.90～1.10:0.90:2.20.
5, CIS according to claim 2 is the making method of powder, it is characterized in that, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be In 2O 3A kind of combination with Ga; This contains M 2Initiator be Se; And CuCl, In 2O 3, Ga and Se volumetric molar concentration be between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
6, CIS according to claim 2 is the making method of powder, it is characterized in that, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be In (NO 3) 3A kind of combination with Ga; This contains M 2Initiator be Se; And CuCl, In (NO 3) 3, Ga and Se volumetric molar concentration be between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
7, CIS according to claim 2 is the making method of powder, it is characterized in that, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Na 2Se; And CuCl, InCl 34H 2O, Ga and Na 2The volumetric molar concentration of Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
8, CIS according to claim 2 is the making method of powder, it is characterized in that, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl 22H 2O; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; And CuCl 22H 2O, InCl 34H 2The volumetric molar concentration of O, Ga and Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
9, wanting 2 described CIS according to right is the making method of powder, it is characterized in that, this mosaic solvent is a dimethyl formamide; This initiator that contains Cu is CuCl 22H 2O; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Na 2Se; And CuCl 22H 2O, InCl 34H 2O, Ga and Na 2The volumetric molar concentration of Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
10, CIS according to claim 2 is the making method of powder, it is characterized in that, this mosaic solvent is a quadrol; This initiator that contains Cu is CuCl; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; And CuCl, InCl 34H 2The volumetric molar concentration of O, Ga and Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
11, CIS according to claim 2 is the making method of powder, it is characterized in that, this mosaic solvent is a quadrol; This initiator that contains Cu is CuCl 22H 2O; This contains M 1Initiator be InCl 34H 2A kind of combination of O and Ga; This contains M 2Initiator be Se; And CuCl 22H 2O, InCl 34H 2The volumetric molar concentration of O, Ga and Se is between 0.90:0.88:0.22:2.20～1.10:0.72:0.18:1.90.
12, CIS according to claim 1 is the making method of powder, it is characterized in that, the rare gas element in this reactive tank is to be selected from following at least a rare gas element: N 2, Ar, or He; The usage quantity of this mosaic solvent be the liquid level of this reactive tank 50%～90% between.
13, CIS according to claim 1 is the making method of powder, it is characterized in that, the reflux temperature in this reactive tank is between 90 ℃～300 ℃; The return time of the parent in this reactive tank is between 4 hours～48 hours.
14, a kind of making method of CIS series target material is characterized in that, the making method of CIS series target material comprises following steps:
(a) inserting according to claim 1～13 a prepared CIS of any one making method in an intravital mould in chamber is powder;
(b) this cavity is reduced pressure to form a purification cavity;
(c) the intravital powder in this chamber is heated up reach a preset temperature and scheduled time of constant temperature;
(d) to this intravital powder in purification chamber boost reach a predetermined pressure and constant voltage should the scheduled time, causing this CIS is powder is obtained the powder densification by this preset temperature and predetermined pressure energy; And
(e) remove this predetermined pressure and in this purification cavity, introduce rare gas element to cool off this purification cavity.
15, the making method of CIS series target material according to claim 14 is characterized in that, the pressure of the purification cavity of this step (b) is 10 -2Torr～10 -5Between the Torr.
16, the making method of CIS series target material according to claim 14 is characterized in that, the temperature rise rate of this step (c) is between 2 ℃/min～10 ℃/min; The rate of pressure rise of this step (d) is between 1MPa/min～3MPa/min.
17, the making method of the target of CIS according to claim 14 system is characterized in that the preset temperature of this step (c) is between 500 ℃～800 ℃; The predetermined pressure of this step (d) is between 60MPa～180MPa; The scheduled time of this step (c), (d) is between 1 hour～8 hours.
CN200810007546A 2008-02-27 2008-02-27 Method for preparing CIS powder and target thereof Pending CN101519307A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102205950A (en) * 2011-04-15 2011-10-05 中南大学 Chalcopyrite-structured CIS powder material and liquid phase preparation method thereof
CN102649542A (en) * 2011-02-23 2012-08-29 威奈联合科技股份有限公司 Production method of chalcopyrite type compound
CN102649543A (en) * 2011-02-23 2012-08-29 威奈联合科技股份有限公司 Manufacture method of chalcopyrite type compounds
CN102712996A (en) * 2010-01-07 2012-10-03 吉坤日矿日石金属株式会社 Sputtering target, compound semiconductor thin film, solar cell having compound semiconductor thin film, and method for manufacturing compound semiconductor thin film
US20120315210A1 (en) * 2011-06-10 2012-12-13 Tokyo Ohka Kogyo Co., Ltd. HYDRAZINE-COORDINATED Cu CHALCOGENIDE COMPLEX AND METHOD OF PRODUCING THE SAME
CN103043629A (en) * 2012-12-19 2013-04-17 中国科学院合肥物质科学研究院 Low-temperature synthesis method for CuGaX2(X=S, se, te) series compounds
CN104953021A (en) * 2014-03-27 2015-09-30 向勇 Method for manufacturing copper, indium, gallium and tellurium thermoelectric conversion material
TWI507362B (en) * 2010-06-22 2015-11-11 Univ Florida Nanocrystalline copper indium diselenide (cis) and ink-based alloys absorber layers for solar cells
CN105405744A (en) * 2010-12-07 2016-03-16 同和控股（集团）有限公司 Chalcogen compound powder, chalcogen compound paste and preparation methods of chalcogen compound powder and chalcogen compound paste

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102712996A (en) * 2010-01-07 2012-10-03 吉坤日矿日石金属株式会社 Sputtering target, compound semiconductor thin film, solar cell having compound semiconductor thin film, and method for manufacturing compound semiconductor thin film
CN102712996B (en) * 2010-01-07 2014-11-26 吉坤日矿日石金属株式会社 Sputtering target, compound semiconductor thin film, solar cell having compound semiconductor thin film, and method for manufacturing compound semiconductor thin film
TWI507362B (en) * 2010-06-22 2015-11-11 Univ Florida Nanocrystalline copper indium diselenide (cis) and ink-based alloys absorber layers for solar cells
CN105405744A (en) * 2010-12-07 2016-03-16 同和控股（集团）有限公司 Chalcogen compound powder, chalcogen compound paste and preparation methods of chalcogen compound powder and chalcogen compound paste
CN102649542A (en) * 2011-02-23 2012-08-29 威奈联合科技股份有限公司 Production method of chalcopyrite type compound
CN102649543A (en) * 2011-02-23 2012-08-29 威奈联合科技股份有限公司 Manufacture method of chalcopyrite type compounds
CN102205950A (en) * 2011-04-15 2011-10-05 中南大学 Chalcopyrite-structured CIS powder material and liquid phase preparation method thereof
CN102205950B (en) * 2011-04-15 2013-03-20 中南大学 Chalcopyrite-structured CIS powder material and liquid phase preparation method thereof
US20120315210A1 (en) * 2011-06-10 2012-12-13 Tokyo Ohka Kogyo Co., Ltd. HYDRAZINE-COORDINATED Cu CHALCOGENIDE COMPLEX AND METHOD OF PRODUCING THE SAME
CN103043629A (en) * 2012-12-19 2013-04-17 中国科学院合肥物质科学研究院 Low-temperature synthesis method for CuGaX2(X=S, se, te) series compounds
CN104953021A (en) * 2014-03-27 2015-09-30 向勇 Method for manufacturing copper, indium, gallium and tellurium thermoelectric conversion material

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