CN104947165B - A kind of preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped - Google Patents
A kind of preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped, it is characterised in that：Prepare the acid solution of bivalent cupric ion salt, the pH value for adjusting solution is faintly acid, make electrolyte, the precursor solution of fluorine is added in the electrolytic solution, then using three-electrode system, using the electro-conductive glass cleaned up as working electrode, Pt pieces are to electrode, saturation KCl Ag/AgCl electrodes are reference electrode, and constant voltage deposits, and prepares the n-type cuprous oxide semiconductive thin film of Fluorin doped.The cuprous oxide film of this Fluorin doped is n-type semiconductor, possesses the porous network structure of uniqueness, and shows good photoelectric properties.Preparation method step provided by the invention is simple, and operation is simple, and reaction condition is gentle, environment-friendly.The n-type cuprous oxide film of the high performance Fluorin doped obtained by simple electrochemical deposition preparation will be widely used on homojunction semiconductor solar cell.
Description
Technical field
The present invention relates to the preparation method of n-type semiconductor film in thin-film solar cells material.Specifically one kind passes through
The predecessor of fluorine, the n-type oxidation of the Fluorin doped prepared using electrochemical deposition means on electro-conductive glass are added into electrolyte
The method of cuprous film.
Background technology
The exploitation that fossil fuel largely makes us to the renewable and environment-friendly energy using a series of problems brought
There is active demand with use.Solar energy is the huge energy depot of clean environment firendly, is sent out using the photovoltaic industry of photoelectric conversion technique
Exhibition is rapid.Wherein, metal-oxide film solar cell has very because prepared by available simple chemical method in cost
Big advantage.Cuprous oxide (Cu2O it is) wherein typically to represent, it is the material non-toxic, abundant inexpensive, it is a kind of potential sun
Photoelectric conversion material.However, the poor photoelectric properties of this material and the unskillful of n-type cuprous oxide technology of preparing limit it
Development in terms of homojunction semiconductor solar cell.
In recent years, to Cu2The research of O modification is relatively more.Wherein, doping is a kind of highly effective means.Study table
It is bright, the Cu of N doping2O films possess the concentration of higher carrier, and the square resistance of film also reduces (Journal of
Applied Physics.2003,93:1-13).Meanwhile the Cu of Cl doping2O(Thin Solid Films.2010,518:
Research 5363-5367) is found, to Cu2O carries out Cl doping, and its conduction type is changed into n-type, the electric conductivity of film by p-type
It is improved.In recent years, Tao etc. (Journal of Applied Physics.2012,111:023709) halogen is reported
(F, Cl, Br) doping n-type Cu2The theoretical calculation of O first principle, the results showed that F, Cl, Br adulterate Cu2O can substitute Cu2O is brilliant
O in lattice, and formation can be all very low, can be stabilized.This and report at present Cl doping Cu2O
(J.Mater.Chem.2011,21:3467-3470；Electrochemical and Solid-State Letters.2009,
12:H89-H91 experimental work) is consistent.
But up to the present, the Cu also without F doping2The report of O film preparations, patent of the present invention have filled up this respect
Blank.And we have found that the cuprous oxide film of Fluorin doped shows n-type semiconductor conduction property, possess the porous of uniqueness
Network structure, while show good photoelectric properties.
Inventive principle and content
The present invention is to utilize electrochemical deposition means, by adding the predecessor of fluorine into electrolyte, on electro-conductive glass
Prepare the n-type cuprous oxide semiconductive thin film of Fluorin doped.In general, electrochemical deposition Cu2O films include two processes.The
One step is the Cu in electrolyte2+Obtain electronics and be reduced to Cu+(equation 1), Cu during this2+Cu (sides may also be reduced to
Journey 2), crucial governing factor therein is exactly the bias of electro-deposition.
Cu2++e-→Cu+ (1)
Cu2++2e-→Cu (2)
Second step is due to Cu+The limitation of solubility in the aqueous solution, Cu+It is converted into Cu2O process (equation 3).Two
The overall reaction of individual process can be represented with equation 4.
2Cu++H2O→Cu2O+2H+ (3)
2Cu2++H2O+2e-→Cu2O+2H+ (4)
When F in electrolyte being present-When, a small amount of Cu+Meeting and F-With reference to generation CuF (equation 5).Because CuF is in aqueous
Solubility very little, in electrolyte a small amount of CuF generation F is doped into Cu2O。
Cu++F-→CuF (5)
It is worth noting that, the amount of the predecessor of the fluorine added in electrolyte can not be too big, before excessive fluorine is added
When driving thing, Ni metal can be obtained.This is probably because the predecessor of fluorine excessive in electrolyte causes more insoluble CuF
It is coated in substrate, have impact on electrolyte environment, cause sedimentation potential to change.
Halogen (F, Cl, Br) adulterates Cu2Theoretical calculation (the Journal of Applied of O first principle
Physics.2012,111:023709) Cu of F doping is found2O can be in Cu2O conduction bands bottom forms a shallow donor doping energy level.
This donor level can be with Reinforced Cu2Absorptions of the O to visible ray, improve the separation of photo-generated carrier.Meanwhile F-Metal is partly led
The pattern of body has regulating and controlling effect.
Inventive principle above, can pass through the test for the cuprous oxide film that Fluorin doped is prepared in electro-conductive glass substrate
Characterize to verify and realize.
Specific embodiments of the present invention are as follows：
The acid solution of bivalent cupric ion salt is prepared, the pH value for adjusting solution is faintly acid, makees electrolyte, is added in the electrolytic solution
Enter the precursor solution of fluorine, then using three-electrode system, using the electro-conductive glass cleaned up as working electrode, Pt pieces are to electricity
Pole, saturation KCl Ag/AgCl electrodes are reference electrode, and constant voltage deposits, and prepares the n-type cuprous oxide semiconductor film of Fluorin doped
Film.
By such scheme, the concentration of bivalent cupric ion salt is 0.005~0.1M in the acid solution of the bivalent cupric ion salt,
Sour concentration for buffering bivalent cupric ion salt is 0.01~0.1M.
By such scheme, the concentration of the precursor solution of fluorine used is 0.005~0.05mol/L.
By such scheme, the bivalent cupric ion salt can be copper formate, copper acetate, propionic acid copper etc., for buffering cupric
The sour formic acid of ion salt, acetic acid etc.；The predecessor of fluorine used is NaF or KF.
By such scheme, between the pH value of solution is 3~6 after the regulation.
By such scheme, the electro-conductive glass as substrate is ito glass or FTO glass, and electro-conductive glass is using
Before, respectively with acetone, ethanol and distilled water immersion are ultrasonic 5 minutes, and ultrasound terminates all to use distilled water flushing every time, finally dries
It is standby.
By such scheme, constant voltage deposition when institute's biasing is+0.01~0.042V (vs. saturations KCl Ag/
AgCl electrodes), 60~80 DEG C of temperature, sedimentation time is 20~60 minutes.
It is described to deposit Cu by such scheme2Being put into mass fraction after electro-conductive glass sample drying after O films is
Two hours are soaked in 0.1%~1% ethanol BTA (azimidobenzene) to keep Cu2O stability.
Beneficial effects of the present invention：
A series of characterization test proves that the cuprous oxide film of this Fluorin doped of the present invention shows n-type semiconductor and led
Electrical property, possesses the porous network structure of uniqueness, and shows good photoelectric properties.With Cu pure with the conditions of2O films
Compare, the cuprous oxide film of Fluorin doped possesses higher carrier concentration and smaller film resistor.This high performance fluorine
The n-type cuprous oxide film of doping will have preferable application prospect on homogeneity junction thin film solar cell.
Brief description of the drawings
The F doping Cu of 1 different dopings of Fig. 1 embodiments2The pattern of O films：(a)：0；(b)：0.005：(c)：
0.01mol/L NaF。
The F doping Cu of 1 different dopings of Fig. 2 embodiments2O films (a)：XRD is composed entirely；(b)：(111) diffraction maximum of amplification
(sample that the addition that i, ii, iii correspond respectively to NaF is 0,0.005 and 0.01mol/L).
Fig. 3 (a) embodiments 1 add 0.01mol/L NaF Cu2O samples F1s before and after sputtering high-resolution XPS collection of illustrative plates；
(before i, ii, iii correspond respectively to sputtering, sputtering 300s and the situation for sputtering 600s) (b) embodiment 1 adds 0 and 0.01mol/L
NaF Cu2The F1s of O samples high-resolution XPS collection of illustrative plates contrast.(addition that i, ii correspond respectively to NaF is 0 and 0.01mol/
L sample)
The F doping Cu of 1 different dopings of Fig. 4 embodiments2O films (a) Mott-Schottky curves；(b) radiation of visible light
Under photocurrent curve figure.(sample that the addition that i, ii, iii correspond respectively to NaF is 0,0.005 and 0.01mol/L)
The F doping Cu of 1 different dopings of Fig. 5 embodiments2The Nyquist figures of O films.(i, ii, iii correspond respectively to NaF
Addition be 0,0.005 and 0.01mol/L sample)
The n-type Cu of the individual layer of Fig. 6 (a) embodiments 12The IV test schematic diagrams of O films；(b) F of 1 different dopings of embodiment
Adulterate Cu2The IV curves (sample that the addition that i, ii, iii correspond respectively to NaF is 0,0.005 and 0.01mol/L) of O films
The IV test schematic diagrams of the homojunction hull cell of Fig. 7 (a) embodiments 1；(b) the F doping of 1 different dopings of embodiment
Cu2The IV curves of the solar cell of O films assembling.(Cell01, Cell02, Cell03 correspond respectively to the addition with NaF
For 0, the homogeneity junction battery of 0.005 and 0.01mol/L sample as n-type semiconductor layer)
The F doping Cu of 2 different dopings of Fig. 8 embodiments2The pattern of O films：(a)：0；(b)：0.01：(c)：
0.015mol/L KF。
The F doping Cu of 2 different dopings of Fig. 9 embodiments2The photocurrent curve figure of O films under visible light illumination.(i,
The sample that the addition that ii, iii correspond respectively to KF is 0,0.01 and 0.015mol/L)
The F doping Cu of 2 different dopings of Figure 10 embodiments2The IV curves of the solar cell of O films assembling.(Cell01,
Cell02, Cell03 are corresponded respectively to using KF addition as 0, and 0.01 and 0.015mol/L sample is as n-type semiconductor layer
Homogeneity junction battery)
The F doping Cu of 3 different dopings of Figure 11 embodiments2The pattern of O films：(a)：0；(b)：0.01：(c)：
0.02mol/L NaF。
The F doping Cu of 3 different dopings of Figure 12 embodiments2The Mott-Schottky curves of O films.(i, ii, iii distinguish
The sample that addition corresponding to NaF is 0,0.01 and 0.02mol/L)
The F doping Cu of 3 different dopings of Figure 13 embodiments2The IV curves of the solar cell of O films assembling.(Cell01,
Cell02, Cell03 are corresponded respectively to using NaF addition as 0, and 0.01 and 0.02mol/L sample is as n-type semiconductor layer
Homogeneity junction battery)
Embodiment
Specific illustration 1：With Cu (Ac)2The Cu of F doping is prepared as electrolyte with HAc2O films
Cu2The preparation of O films is carried out in thermostat water bath.Ito glass is first cleaned before preparing, and (size is 2 × 5cm2)：
Acetone is used respectively, and ethanol and distilled water immersion are ultrasonic 5 minutes, and ultrasound terminates all to use distilled water flushing every time, then drying for standby.
Prepare 0.02mol/L Cu (Ac)2For HAc mixed solutions with 0.08mol/L as electrolyte, volume is 100mL.Use 4mol/L
NaOH solution adjusts pH, during being somebody's turn to do, is continuously agitated with magneton, while alkali lye showing to pH meter is slowly added dropwise with rubber head dropper
Number is stable 4.9 or so.Predecessors of 0.005, the 0.01mol/L NaF as fluorine is added into electrolyte respectively, then will electrolysis
Liquid, which is put into water-bath, is heated to 70 DEG C.Using three-electrode system, using the ito glass cleaned up as working electrode, Pt pieces are
To electrode, saturation KCl Ag/AgCl electrodes are reference electrode, and constant voltage deposition, constant voltage deposition when institute's biasing is+0.02V
(vs. saturations KCl Ag/AgCl electrodes), sedimentation time is 30 minutes.After completion of the reaction, ito glass is taken out, is washed with distillation
Wash.It is put into after sample drying in the ethanol BTA (azimidobenzene) that mass fraction is 0.1% and soaks two hours to keep Cu2O's is steady
It is qualitative.Separately experiment is compared to be not added with NaF solution.
The F doping Cu of the above-mentioned different dopings being prepared2The electromicroscopic photograph and X ray diffracting spectrum of O thin-film materials
Respectively as shown in Fig. 1 and Fig. 2.The Cu of gained2O films direct growth from ITO substrate forms, and is combined with glass substrate
Closely.After adding NaF into electrolyte as seen from Figure 1, Cu2The pattern of O films by typical dendroid by
Gradually it is changed into porous netted.It is believed that this porous network structure causes film to possess bigger specific surface area, favorably
In visible ray absorption and electric charge body phase transfer.F adulterates Cu as shown in Figure 22O thing does not change mutually, is all pure
The Cu of phase2O.The most strong diffraction maximum of three samples is contrasted, (111) peak for adding NaF sample is offset to wide-angle direction.
We further prove that F is doped into Cu by x-ray photoelectron power spectrum2O lattices, as a result as shown in Figure 3.Fig. 3 (a)
It is the maximum sample F1s before and after sputtering of F dopings high-resolution power spectrum.Before sputtering, 685eV and 687eV can be equal in combination
Two peaks at place correspond to Cu respectively2In O lattices F ion and sample surfaces absorption F ion, and sample be sputtered 300s and
Combination is only remained after 600s can be equal to 685eV peak.This explanation F has been doped into Cu2O, while can not also be kept away in sample surfaces
Part F ion has been adsorbed with exempting from.Figure (b) is the maximum sample of doping and pure Cu2O F1s high-resolution XPS collection of illustrative plates, it is right
Than can further prove that F is doped into Cu2O lattices.
The electric current that the conduction type of semiconductor can generally be opened by Mott-Schottky slope of a curves and pulsed light
The direction of mutation judges.The Cu of three different F dopings in Fig. 4 (a)2The Mott-Schottky curves of O film sample samples
Slope be all on the occasion of, this show we prepare sample be all n-type semiconductor.Further from Fig. 4 (b), in pulsed light
The moment of unlatching, three Cu2The electric current of O film samples is mutated to high current direction, generates a positive photoelectric current, is showed
Go out the property of n-type semiconductor.Thus we judge the Cu of the obtained F doping on ITO substrates2O films are n-type Cu2O.In addition,
By Mott-Schottky curves, we can also calculate carrier concentration.It is respectively 0 for the amount for adding NaF,
0.005,0.01mol/L three samples, it is 6.18 × 10 respectively that its electron concentration, which calculates result,16,1.49×1017With 9.25
×1017cm-3.It can be seen that the Cu of F doping2O carrier concentration is greatly improved, the maximum sample of F dopings
Carrier concentration is pure Cu2Ten times of O are more than.This is primarily due to the Cu of F doping2F atom substitutes O atom in O, can provide
Extra electronics, while form a shallow donor doping energy level at conduction band bottom.From Fig. 4 (b) it can also be seen that what F was adulterated
Cu2O photoelectric current has also obtained certain lifting.
Electrochemical impedance spectroscopy is the separation of the powerful of research material electrochemical behavior, particularly electric charge, and electric charge is caught
Obtain the processes such as the electric charge transfer with interface.Fig. 5 is three Cu2The Nyquist figures of O film samples, the semicircle radius of its electric capacity arc
The interfacial charge transfer resistance of film sample and solution can be reflected.It can be seen that with the increase of F dopings, semicircle radius
Reducing, i.e., solid-liquid interface charge transfer resistance reduces.
In order to further investigate the Cu of F doping2The electric conductivity of O films, we have plated gold electrode in sample surfaces, enter
IV tests are gone, as a result as shown in Figure 6.Fig. 6 is represented：Three samples possess linear IV curves well, show sample and conduction
Good Ohmic contact is formd before substrate of glass, this provides the foundation to prepare homogeneity joint solar cell.Meanwhile according to
The slope of straight line can see, the Cu of F doping2O films possess smaller resistance, and electric conductivity is more excellent.Then, Wo Men
One layer of p-type Cu of continuous electro-deposition on ITO electro-conductive glass2O films and the n-type Cu of F doping2O films, plate gold electrode, are assembled into
Homogeneity junction battery, IV tests are carried out.IV curves as shown in Figure 7, be shown in by the Photovoltaic measurement data of three homogeneity joint solar cells
Shown in table 1, table 1 is the Photovoltaic measurement data of 1 three homogeneity joint solar cells of embodiment.(Cell01,Cell02,Cell03
Correspond respectively to using NaF addition as 0,0.005 and 0.01mol/L sample is electric as the homojunction of n-type semiconductor layer
Pond).With the Cu without doping2O films are compared, the Cu adulterated with F2Light of the O films as the homogeneity junction battery of n-type semiconductor layer
Photoelectric transformation efficiency is greatly improved.Wherein, Cell03 photoelectric transformation efficiency is as many as seven times of Cell01.
Table 1
Specific illustration 2：The Cu of F doping is prepared using copper formate and acetic acid as electrolyte2O films
Cu2The preparation of O films is carried out in thermostat water bath.Ito glass is first cleaned before preparing, and (size is 2 × 5cm2)：
Acetone is used respectively, and ethanol and distilled water immersion are ultrasonic 5 minutes, and ultrasound terminates all to use distilled water flushing every time, then drying for standby.
Prepare 0.05mol/L Cu (HCOO)2For HAC mixed solutions with 0.1mol/L as electrolyte, volume is 100mL.Use 4mol/
L NaOH solutions adjust pH, during being somebody's turn to do, are continuously agitated with magneton, while alkali lye is slowly added dropwise to pH meter with rubber head dropper
Registration is stable 4.0 or so.Predecessors of 0.01, the 0.015mol/L KF as fluorine is added into electrolyte respectively, then will electrolysis
Liquid, which is put into water-bath, is heated to 60 DEG C.Using three-electrode system, using the ito glass cleaned up as working electrode, Pt pieces are
To electrode, saturation KCl Ag/AgCl electrodes are reference electrode, constant voltage deposition, constant voltage deposition when institute's biasing is+
0.025V (vs. saturations KCl Ag/AgCl electrodes), sedimentation time is 25 minutes.After completion of the reaction, ito glass is taken out, with steaming
Distilled water is washed.It is put into after sample drying in the ethanol BTA (azimidobenzene) that mass fraction is 0.5% and soaks two hours to keep
Cu2O stability.Separately experiment is compared to be not added with NaF solution.
The Cu being prepared2The electromicroscopic photograph of O thin-film materials is as shown in Figure 8.It is similar with illustration 1, it can be seen that to electrolysis
After KF being added in liquid, Cu2The pattern of O films is gradually converted into porous netted by typical dendroid.With in illustration 1
Electromicroscopic photograph is compared, and cavernous structure here is finer and close, and aperture is smaller.It is believed that this porous network structure cause it is thin
Film possesses bigger specific surface area, be advantageous to visible ray absorption and electric charge body phase transfer.
We judge the conduction type of semiconductor by the direction of the current break of pulsed light unlatching.As shown in Figure 9, exist
The moment that pulsed light is opened, three Cu2The electric current of O film samples is mutated to high current direction, generates a positive photoelectricity
Stream, show the property of n-type semiconductor.Thus we judge the Cu of the obtained F doping on ITO substrates2O films are n-types
Cu2O.Meanwhile the it may be seen that Cu of F doping2The photoelectric current of O films has also obtained certain lifting.Then, we are mixed with F
Miscellaneous Cu2O films are assembled into homogeneity junction battery as n-type semiconductor layer, have carried out IV tests.IV curves as shown in Figure 10, three
The Photovoltaic measurement data of individual homogeneity joint solar cell are shown in Table 2.The light of the 2 three homogeneity joint solar cells of embodiment of table 2
Lie prostrate measurement data.(Cell01, Cell02, Cell03 are corresponded respectively to using KF addition as 0,0.01 and 0.015mol/L's
Homogeneity junction battery of the sample as n-type semiconductor layer).The Cu adulterated with F2Homogeneity junction battery of the O films as n-type semiconductor layer
Photoelectric transformation efficiency it is higher 1-4 times than no doping.
Table 2
Specific illustration 3：The Cu of F doping is prepared using propionic acid copper and acetic acid as electrolyte2O films
Cu2The preparation of O films is carried out in thermostat water bath.FTO glass is first cleaned before preparing, and (size is 2 × 5cm2)：
Acetone is used respectively, and ethanol and distilled water immersion are ultrasonic 5 minutes, and ultrasound terminates all to use distilled water flushing every time, then drying for standby.
0.08mol/L propionic acid copper and 0.1mol/L acetic acid mixed solution are prepared as electrolyte, volume is 100mL.Use 4mol/L
NaOH solution adjusts pH, during being somebody's turn to do, is continuously agitated with magneton, while alkali lye showing to pH meter is slowly added dropwise with rubber head dropper
Number is stable 4.0 or so.Add predecessors of 0.01, the 0.02mol/L NaF as fluorine into electrolyte respectively, then by electrolyte
It is put into water-bath and is heated to 60 DEG C.Using three-electrode system, using the ito glass cleaned up as working electrode, Pt pieces are pair
Electrode, saturation KCl Ag/AgCl electrodes are reference electrode, and constant voltage deposition, constant voltage deposition when institute's biasing is+0.015V
(vs. saturations KCl Ag/AgCl electrodes), sedimentation time is 30 minutes.After completion of the reaction, FTO glass is taken out, is washed with distillation
Wash.It is put into after sample drying in the ethanol BTA (azimidobenzene) that mass fraction is 1% and soaks two hours to keep Cu2O stabilization
Property.Separately experiment is compared to be not added with NaF solution.
The Cu being prepared2The electromicroscopic photograph of O thin-film materials is as shown in Figure 11.For no addition NaF sample, its shape
Looks show the stone-like of no corner angle, different with the dendroid in illustration 1 and 2, and the change of this and substrate and experiment condition has
Relation.Similarly, after adding NaF into electrolyte, Cu2The pattern of O films is gradually changed into porous netted.It can see
Arrive, the F doping Cu under the conditions of being somebody's turn to do2The network structure of O films (0.02mol/L NaF) is more obvious.It is it is believed that this porous
Network structure cause film to possess bigger specific surface area, be advantageous to visible ray absorption and electric charge body phase transfer.
We judge the conduction type of semiconductor by Mott-Schottky slope of a curves.Three samples in Figure 12
Mott-Schottky slope of a curves be all on the occasion of, show we prepare sample be all n-type semiconductor.In addition, pass through
Mott-Schottky slope of a curve sizes can be seen that the Cu for F doping2The carrier concentration of O samples has obtained carrying greatly very much
Rise.This is primarily due to the Cu of F doping2F atom substitutes O atom in O, can provide extra electronics, while formed at conduction band bottom
One shallow donor doping energy level.The Cu adulterated with F2O films are assembled into the IV curves of homogeneity junction battery as n-type semiconductor layer
As shown in Figure 13, Photovoltaic measurement data are shown in Table 3.The Photovoltaic measurement number of table 3 embodiment, 3 three homogeneity joint solar cells
According to.(Cell01, Cell02, Cell03 are corresponded respectively to using NaF addition as 0, and 0.01 and 0.02mol/L sample is as n
The homogeneity junction battery of type semiconductor layer).The Cu adulterated by F2The efficiency for the homojunction solar cell that O thin film semiconductors are assembled into
It is undoped with Cu2As many as 5 times of O homojunction solar cells.
Table 3
Specific illustration 4：The Cu of F doping is prepared using copper acetate and formic acid as electrolyte2O films
Cu2The preparation of O films is carried out in thermostat water bath.FTO glass is first cleaned before preparing, and (size is 2 × 5cm2)：
Acetone is used respectively, and ethanol and distilled water immersion are ultrasonic 5 minutes, and ultrasound terminates all to use distilled water flushing every time, then drying for standby.
0.1mol/L copper acetate and 0.05mol/L formic acid mixed solution are prepared as electrolyte, volume is 100mL.Use 4mol/L
NaOH solution adjusts pH, during being somebody's turn to do, is continuously agitated with magneton, while alkali lye showing to pH meter is slowly added dropwise with rubber head dropper
Number is stable 6.0 or so.Predecessors of 0.025, the 0.05mol/L NaF as fluorine is added into electrolyte respectively, then will electrolysis
Liquid, which is put into water-bath, is heated to 80 DEG C.Using three-electrode system, using the ito glass cleaned up as working electrode, Pt pieces are
To electrode, saturation KCl Ag/AgCl electrodes are reference electrode, and constant voltage deposition, constant voltage deposition when institute's biasing is+0.04V
(vs. saturations KCl Ag/AgCl electrodes), sedimentation time is 20 minutes.After completion of the reaction, FTO glass is taken out, is washed with distillation
Wash.It is put into after sample drying in the ethanol BTA (azimidobenzene) that mass fraction is 1% and soaks two hours to keep Cu2O stabilization
Property.Separately experiment is compared to be not added with NaF solution.
With illustration 1,2 as 3, due to the regulating and controlling effect of F ion, the Cu for the F doping being prepared under the conditions of being somebody's turn to do2O is thin
Porous netted pattern is presented in film.This porous network structure causes film to possess bigger specific surface area, is advantageous to visible
The transfer of the absorption of light and electric charge in body phase.Optical electro-chemistry test demonstrates the Cu for the F doping being prepared under the conditions of this2O is thin
Film possesses bigger photoelectric current and carrier concentration, and the performance of battery is also greatly improved.
Claims (5)
- A kind of 1. preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped, it is characterised in that：Prepare bivalent cupric ion salt Acid solution, adjust solution pH value be 3 ~ 4.9, make electrolyte, in the electrolytic solution add fluorine precursor solution, then utilize Three-electrode system, using the electro-conductive glass cleaned up as working electrode, Pt pieces are to be to electrode, saturation KCl Ag/AgCl electrodes Reference electrode, constant voltage deposit, and prepare the n-type cuprous oxide semiconductive thin film of Fluorin doped；The concentration of the precursor solution of fluorine used is 0.005 ~ 0.05mol/L；Constant voltage deposition when institute's biasing is+0.01 ~ 0.042V, relative to saturation KCl Ag/AgCl electrodes, temperature 60 ~ 80 DEG C, sedimentation time is 20 ~ 60 minutes.
- 2. the preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped according to claim 1, it is characterised in that： The concentration of bivalent cupric ion salt is 0.005 ~ 0.1M in the acid solution of the bivalent cupric ion salt, for buffering bivalent cupric ion salt Sour concentration be 0.01 ~ 0.1M.
- 3. the preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped according to claim 1, it is characterised in that： The bivalent cupric ion salt can be copper formate, copper acetate, propionic acid copper, and the acid for buffering bivalent cupric ion salt can be formic acid, second Acid；The predecessor of fluorine used is NaF or KF.
- 4. the preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped according to claim 1, it is characterised in that： The electro-conductive glass as substrate is ito glass or FTO glass, electro-conductive glass before the use, respectively with acetone, ethanol Ultrasonic 5 minutes with distilled water immersion, ultrasound terminates all to use distilled water flushing, last drying for standby every time.
- 5. the preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped according to claim 1, it is characterised in that： It is described to deposit Cu2It is put into the ethanol BTA that mass fraction is 0.1% ~ 1% and soaks after electro-conductive glass sample drying after O films Two hours to keep Cu2O stability.
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| CN105696047A (en) * | 2016-01-26 | 2016-06-22 | 太原理工大学 | Rapid preparation method for cuprous oxide nano-film |
| CN106129174B (en) * | 2016-07-07 | 2017-08-29 | 深圳大学 | A kind of fluorine doped cuprous oxide film and preparation method thereof |
| CN108796532B (en) * | 2017-05-03 | 2020-06-16 | 天津大学 | Nickel oxide-cuprous oxide homojunction photocathode, preparation method thereof and application thereof in photocatalysis |
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| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
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| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
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| 《Cu2O半导体薄膜在酸性条件下的电化学沉积》;胡飞，等;《功能材料》;20110620;第42卷;第488、490页，图3 * |
| 《Electrochemical deposition of Cl-doped n-type Cu2O on reduced grapheme oxide electrodes》;Shixin Wu等;《Journal of Materials Chemistry》;20101215;第21卷;第3467-3470页 * |
| 《n-type doping in Cu2O with F, Cl, and Br: A first-principles study》;Qiong Bai等;《Journal of Applied Physics》;20120125;第111卷;第023709-3页 * |
| 《溶液温度和衬底对电化学沉积Cu2O薄膜形貌的影响》;陈志钢，等;《材料科学与工程学报》;20050820;第23卷(第4期);第570-573页 * |
| Characterization of Cl-doped n-type Cu2O prepared by electrodeposition;Xiaofei Han等;《Thin Solid films》;20100330;第518卷(第19期);第5363页 * |
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