CN104947165A - Production method of fluorine-doped n type cuprous oxide semiconductor film - Google Patents
Production method of fluorine-doped n type cuprous oxide semiconductor film Download PDFInfo
- Publication number
- CN104947165A CN104947165A CN201510288549.XA CN201510288549A CN104947165A CN 104947165 A CN104947165 A CN 104947165A CN 201510288549 A CN201510288549 A CN 201510288549A CN 104947165 A CN104947165 A CN 104947165A
- Authority
- CN
- China
- Prior art keywords
- oxide semiconductor
- semiconductor film
- fluorine
- film
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
The invention relates to a production method of a fluorine-doped n type cuprous oxide semiconductor film. The method comprises the following steps: preparing an acid solution of a bivalent copper ion salt, adjusting the solution to be weakly acidic, adding a fluorine precursor solution to the weakly acidic solution used as an electrolyte, using a three-electrode system adopting cleaned conductive glass as a working electrode, a Pt slice as a counter electrode and Ag/AgCl electrode of saturated KCl as a reference electrode, and carrying out constant voltage deposition to produce the fluorine-doped n type cuprous oxide semiconductor film. The fluorine-doped cuprous oxide film is an n type semiconductor, has a unique porous netted structure, and has very good photoelectric performances. The production method has the advantages of simple steps, simple operation, mild reaction conditions and environmental protection. The high-performance fluorine-doped n type cuprous oxide semiconductor film obtained through the simple electrochemical deposition production method will be widely applied in homojunction semiconductor solar batteries.
Description
Technical field
The present invention relates to the preparation method of n-type semiconductor film in thin-film solar cells material.Specifically by adding a precursor for fluorine in electrolytic solution, the method for the N-shaped cuprous oxide film of the Fluorin doped utilizing electrochemical deposition means to prepare on conductive glass.
Background technology
Fossil oil uses the series of problems brought to make us have active demand to the exploitation of the renewable and eco-friendly energy and use in a large number.Sun power is the huge energy depot of clean environment firendly, utilizes the theCourse of PV Industry of photoelectric conversion technique rapid.Wherein, metal oxide film solar cell due to available simple chemical method preparation on cost tool have great advantage.Red copper oxide (Cu
2o) being wherein typically represent, this material non-toxic, enriching inexpensive, is a kind of potential solar photoelectric transition material.But the photoelectric properties that this material is poor and N-shaped Red copper oxide technology of preparing unskillful limits its development in homojunction semiconductor solar cell.
In recent years, to Cu
2the research of the modification of O is many.Wherein, doping is a kind of highly effective means.Research shows, the Cu of N doping
2o film has the concentration of higher current carrier, and the square resistance of film also reduces (Journal of Applied Physics.2003,93:1-13).Meanwhile, the Cu of Cl doping
2the research of O (Thin Solid Films.2010,518:5363-5367) finds, to Cu
2o carries out Cl doping, and its conduction type changes N-shaped into by p-type, and the electroconductibility of film have also been obtained raising.In recent years, Tao etc. (Journal of Applied Physics.2012,111:023709) report halogen (F, Cl, Br) Doped n-type Cu
2the Theoretical Calculation of the first principle of O, result shows F, Cl, Br doped with Cu
2o can substitute Cu
2o in O lattice, and formation can be all very low, can stable existence.This Cu adulterated with the Cl reported at present
2o (J.Mater.Chem.2011,21:3467-3470; Electrochemical and Solid-State Letters.2009,12:H89-H91) cut-and-try work conform to.
But the Cu up to the present, also not having F to adulterate
2the report of O film preparation, patent of the present invention has filled up the blank of this respect.And we find that the cuprous oxide film of Fluorin doped shows n-type semiconductor conduction property, have unique porous network structure, show good photoelectric properties simultaneously.
Inventive principle and content
The present invention utilizes electrochemical deposition means, by adding the precursor of fluorine in electrolytic solution, conductive glass is prepared the N-shaped Red copper oxide semiconductor film of Fluorin doped.Generally speaking, electrochemical deposition Cu
2o film comprises two processes.The first step is the Cu in electrolytic solution
2+obtain electronics and be reduced to Cu
+(equation 1), Cu in this process
2+also may be reduced to Cu (equation 2), crucial controlling factor is wherein exactly the bias voltage of galvanic deposit.
Cu
2++e
-→Cu
+(1)
Cu
2++2e
-→Cu (2)
Second step is due to Cu
+the restriction of the solubleness in the aqueous solution, Cu
+be converted into Cu
2the process (equation 3) of O.The total reaction of two processes can represent with equation 4.
2Cu
++H
2O→Cu
2O+2H
+(3)
2Cu
2++H
2O+2e
-→Cu
2O+2H
+(4)
When there is F in electrolytic solution
-time, a small amount of Cu
+meeting and F
-in conjunction with generation CuF (equation 5).Because CuF solubleness is in aqueous very little, in electrolytic solution, the generation of a small amount of CuF makes F be doped into Cu
2o.
Cu
++F
-→CuF (5)
It should be noted that the amount of the precursor of the fluorine added in electrolytic solution can not be too large, when adding the precursor of too much fluorine, can Ni metal be obtained.This may be because the precursor of fluorine excessive in electrolytic solution makes more insoluble CuF be coated in substrate, have impact on electrolytic solution environment, causes sedimentation potential to change.
Halogen (F, Cl, Br) doped with Cu
2the Theoretical Calculation (Journal of Applied Physics.2012,111:023709) of the first principle of O finds the Cu that F adulterates
2o can at Cu
2a shallow donor doping energy level is formed at the bottom of O conduction band.This donor level can Reinforced Cu
2o, to the absorption of visible ray, improves the separation of photo-generated carrier.Meanwhile, F
-regulating and controlling effect is had to the pattern of metal semiconductor.
Above inventive principle, can be characterized by the test preparing the cuprous oxide film of Fluorin doped in conductive glass substrate and verify and realize.
Specific embodiment of the invention scheme is as follows:
The acid solution of preparation bivalent cupric ion salt, the pH value of regulator solution is slightly acidic, make electrolytic solution, add the precursor solution of fluorine in the electrolytic solution, then utilize three-electrode system, with the conductive glass cleaned up for working electrode, Pt sheet is to electrode, the Ag/AgCl electrode of saturated KCl is reference electrode, and constant voltage deposits, and prepares the N-shaped Red copper oxide semiconductor film of Fluorin doped.
By such scheme, in the acid solution of described bivalent cupric ion salt, the concentration of bivalent cupric ion salt is 0.005 ~ 0.1M, is 0.01 ~ 0.1M for cushioning the concentration of the acid of bivalent cupric ion salt.
By such scheme, the concentration of the precursor solution of fluorine used is 0.005 ~ 0.05mol/L.
By such scheme, described bivalent cupric ion salt can be Tubercuprose, neutralized verdigris, propionic acid copper etc., for cushioning the sour formic acid, acetic acid etc. of bivalent cupric ion salt; The precursor of fluorine used is NaF or KF.
By such scheme, after described adjustment, the pH value of solution is between 3 ~ 6.
By such scheme, the described conductive glass as substrate is ito glass or FTO glass, and conductive glass before the use, uses acetone respectively, and ethanol and ultrasonic 5 minutes of distilled water immersion, each ultrasonic end all uses distilled water flushing, and final drying is for subsequent use.
By such scheme, described constant voltage deposition time institute's biasing is+0.01 ~ 0.042V (the Ag/AgCl electrode of the saturated KCl of vs.), and temperature 60 ~ 80 DEG C, depositing time is 20 ~ 60 minutes.
By such scheme, describedly Cu will be deposited
2put into after conductive glass sample drying after O film massfraction be 0.1% ~ 1% ethanol BTA (azimidobenzene) soak two hours to keep Cu
2the stability of O.
Beneficial effect 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 conduction property, has unique porous network structure, and shows good photoelectric properties.With Cu pure under same condition
2o film is compared, and the cuprous oxide film of Fluorin doped has higher carrier concentration and less sheet resistance.The N-shaped cuprous oxide film of this high performance Fluorin doped will have good application prospect in homojunction thin-film solar cells.
Accompanying drawing explanation
The F doped with Cu of the different doping of Fig. 1 embodiment 1
2the pattern of O film: (a): 0; (b): 0.005:(c): 0.01mol/L NaF.
The F doped with Cu of the different doping of Fig. 2 embodiment 1
2o film (a): XRD composes entirely; (b): (111) diffraction peak of amplification (addition that i, ii, iii correspond respectively to NaF is the sample of 0,0.005 and 0.01mol/L).
Fig. 3 (a) embodiment 1 adds the Cu of 0.01mol/L NaF
2the high resolution XPS collection of illustrative plates of O sample F1s before and after sputtering; (before i, ii, iii correspond respectively to sputtering, the situation of sputtering 300s and sputtering 600s) (b) embodiment 1 adds the Cu of 0 and 0.01mol/L NaF
2the high resolution XPS collection of illustrative plates contrast of the F1s of O sample.(addition that i, ii correspond respectively to NaF is the sample of 0 and 0.01mol/L)
The F doped with Cu of the different doping of Fig. 4 embodiment 1
2o film (a) Mott-Schottky curve; Photocurrent curve figure under (b) radiation of visible light.(addition that i, ii, iii correspond respectively to NaF is the sample of 0,0.005 and 0.01mol/L)
The F doped with Cu of the different doping of Fig. 5 embodiment 1
2the Nyquist figure of O film.(addition that i, ii, iii correspond respectively to NaF is the sample of 0,0.005 and 0.01mol/L)
The N-shaped Cu of Fig. 6 (a) embodiment 1 individual layer
2the IV of O film tests schematic diagram; The F doped with Cu of the different doping of (b) embodiment 1
2the IV curve of O film (addition that i, ii, iii correspond respectively to NaF is the sample of 0,0.005 and 0.01mol/L)
The IV of Fig. 7 (a) embodiment 1 homojunction hull cell tests schematic diagram; The F doped with Cu of the different doping of (b) embodiment 1
2the IV curve of the solar cell of O film assembling.(Cell01, Cell02, Cell03 correspond respectively to the addition of NaF for 0,0.005 and the sample of 0.01mol/L as the homojunction battery of n-type semiconductor layer)
The F doped with Cu of the different doping of Fig. 8 embodiment 2
2the pattern of O film: (a): 0; (b): 0.01:(c): 0.015mol/L KF.
The F doped with Cu of the different doping of Fig. 9 embodiment 2
2o film photocurrent curve figure under visible light illumination.(addition that i, ii, iii correspond respectively to KF is the sample of 0,0.01 and 0.015mol/L)
The F doped with Cu of the different doping of Figure 10 embodiment 2
2the IV curve of the solar cell of O film assembling.(Cell01, Cell02, Cell03 correspond respectively to the addition of KF for 0,0.01 and the sample of 0.015mol/L as the homojunction battery of n-type semiconductor layer)
The F doped with Cu of the different doping of Figure 11 embodiment 3
2the pattern of O film: (a): 0; (b): 0.01:(c): 0.02mol/L NaF.
The F doped with Cu of the different doping of Figure 12 embodiment 3
2the Mott-Schottky curve of O film.(addition that i, ii, iii correspond respectively to NaF is the sample of 0,0.01 and 0.02mol/L)
The F doped with Cu of the different doping of Figure 13 embodiment 3
2the IV curve of the solar cell of O film assembling.(Cell01, Cell02, Cell03 correspond respectively to the addition of NaF for 0,0.01 and the sample of 0.02mol/L as the homojunction battery of n-type semiconductor layer)
Embodiment
Concrete illustration 1: with Cu (Ac)
2with HAc as electrolytic solution prepare F doping Cu
2o film
Cu
2the preparation of O film carries out in thermostat water bath.(size is 2 × 5cm first to clean ito glass before preparation
2): use acetone respectively, ethanol and ultrasonic 5 minutes of distilled water immersion, each ultrasonic end all uses distilled water flushing, then drying for standby.The Cu (Ac) of preparation 0.02mol/L
2with the HAc mixing solutions of 0.08mol/L as electrolytic solution, volume is 100mL.Regulate pH by 4mol/L NaOH solution, in this process, ceaselessly stir with magneton, slowly drip alkali lye to the registration of pH meter with glue head dropper simultaneously and be stabilized in about 4.9.Respectively to adding the precursor of 0.005,0.01mol/L NaF as fluorine in electrolytic solution, then electrolytic solution is put into water-bath and be heated to 70 DEG C.Utilize three-electrode system, with the ito glass cleaned up for working electrode, Pt sheet is to electrode, the Ag/AgCl electrode of saturated KCl is reference electrode, constant voltage deposits, constant voltage deposition time institute's biasing is+0.02V (the Ag/AgCl electrode of the saturated KCl of vs.), and depositing time is 30 minutes.After completion of the reaction, take out ito glass, use distilled water wash.Put into after sample drying massfraction be 0.1% ethanol BTA (azimidobenzene) soak two hours to keep Cu
2the stability of O.Separately compare test not add NaF solution.
The F doped with Cu of the above-mentioned different dopings prepared
2the electromicroscopic photograph of O thin-film material and X ray diffracting spectrum are shown in shown in Fig. 1 and Fig. 2 respectively.The Cu of gained
2o film forms from direct growth ITO substrate, is combined closely with glass substrate.After adding NaF as seen from Figure 1 in electrolytic solution, Cu
2the pattern of O film changes the netted of porous into gradually by typical dendroid.We think, the reticulated structure of this porous makes film have larger specific surface area, are conducive to the transfer in body phase of the absorption of visible ray and electric charge.F doped with Cu as shown in Figure 2
2the thing of O does not change mutually, is all the Cu of pure phase
2o.The strongest diffraction peak of contrast three samples, (111) peak adding the sample of NaF offsets to wide-angle direction.
By x-ray photoelectron power spectrum, we prove that F is doped into Cu further
2o lattice, the results are shown in Figure shown in 3.Fig. 3 (a) is the high resolution power spectrum of the maximum sample of F doping F1s before and after sputtering.Before sputtering, combining two peaks corresponding Cu respectively that can equal 685eV and 687eV place
2the F ion of F ion and sample surfaces absorption in O lattice, and sample only remains the peak combining and can equal 685eV after sputtered 300s and 600s.This illustrates that F has been doped into Cu
2o, has also inevitably adsorbed part F ion at sample surfaces simultaneously.Figure (b) is the maximum sample of doping and pure Cu
2the high resolution XPS collection of illustrative plates of the F1s of O, contrast can prove that F is doped into Cu further
2o lattice.
The direction of the current break that the conduction type of semi-conductor can be opened by Mott-Schottky slope of a curve and pulsed light usually judges.The Cu of three different F dopings in Fig. 4 (a)
2the Mott-Schottky slope of a curve of O film sample sample be all on the occasion of, this shows that the sample that we prepare is all n-type semiconductor.Further from Fig. 4 (b), in the moment that pulsed light is opened, three Cu
2the electric current of O film sample, to the sudden change of high current direction, creates a positive photoelectric current, shows the character of n-type semiconductor.We judge the Cu of F doping obtained on ITO substrate thus
2o film is N-shaped Cu
2o.In addition, by Mott-Schottky curve, we can also calculate carrier concentration.The amount adding NaF is respectively to three samples of 0,0.005,0.01mol/L, it is 6.18 × 10 respectively that its electron density calculates result
16, 1.49 × 10
17with 9.25 × 10
17cm
-3.Can see, the Cu of F doping
2the carrier concentration of O is greatly improved, and the carrier concentration of the sample that F doping is maximum is pure Cu
2ten times of O more than.This is mainly because the Cu of F doping
2in O, F atom substitutes O atom, can provide extra electronics, at the bottom of conduction band, form a shallow donor doping energy level simultaneously.Also can see from Fig. 4 (b), the Cu of F doping
2the photoelectric current of O have also been obtained certain lifting.
Electrochemical impedance spectroscopy is the separation of the powerful of research material electrochemical behavior, particularly electric charge, catching and the processes such as the Charger transfer at interface of electric charge.Fig. 5 is three Cu
2the Nyquist figure of O film sample, the semicircle radius of its electric capacity arc can reflect the interfacial charge transfer resistance of film sample and solution.Can see, along with the increase of F doping, semicircle radius is in reduction, and namely solid-liquid interface charge transfer resistance reduces.
In order to investigate the Cu of F doping further
2the conductivity of O film, we have plated gold electrode at sample surfaces, have carried out IV test, the results are shown in Figure shown in 6.Fig. 6 represents: three samples have well linear IV curve, define good ohmic contact before showing sample and conductive glass substrate, and this provides the foundation for preparing homojunction solar cell.Meanwhile, the slope according to straight line can be seen, the Cu of F doping
2o film has less resistance, and conductivity is more excellent.Subsequently, our continuous electro-deposition one deck p-type Cu on ITO conductive glass
2the N-shaped Cu of O film and F doping
2o film, plated with gold electrode, is assembled into homojunction battery, has carried out IV test.As shown in Figure 7, the Photovoltaic measurement data of three homojunction solar cells are shown in Table 1 IV curve, and table 1 is the Photovoltaic measurement data of embodiment 1 three homojunction solar cells.(Cell01, Cell02, Cell03 correspond respectively to the addition of NaF for 0,0.005 and the sample of 0.01mol/L as the homojunction battery of n-type semiconductor layer).With the Cu do not adulterated
2o film is compared, with the Cu of F doping
2o film is greatly improved as the photoelectric transformation efficiency of the homojunction battery of n-type semiconductor layer.Wherein, the photoelectric transformation efficiency of Cell03 is seven times more than of Cell01.
Table 1
Concrete illustration 2: prepare the Cu of F doping as electrolytic solution using Tubercuprose and acetic acid
2o film
Cu
2the preparation of O film carries out in thermostat water bath.(size is 2 × 5cm first to clean ito glass before preparation
2): use acetone respectively, ethanol and ultrasonic 5 minutes of distilled water immersion, each ultrasonic end all uses distilled water flushing, then drying for standby.The Cu (HCOO) of preparation 0.05mol/L
2with the HAC mixing solutions of 0.1mol/L as electrolytic solution, volume is 100mL.Regulate pH by 4mol/L NaOH solution, in this process, ceaselessly stir with magneton, slowly drip alkali lye to the registration of pH meter with glue head dropper simultaneously and be stabilized in about 4.0.Respectively to adding the precursor of 0.01,0.015mol/L KF as fluorine in electrolytic solution, then electrolytic solution is put into water-bath and be heated to 60 DEG C.Utilize three-electrode system, with the ito glass cleaned up for working electrode, Pt sheet is to electrode, the Ag/AgCl electrode of saturated KCl is reference electrode, constant voltage deposits, constant voltage deposition time institute's biasing is+0.025V (the Ag/AgCl electrode of the saturated KCl of vs.), and depositing time is 25 minutes.After completion of the reaction, take out ito glass, use distilled water wash.Put into after sample drying massfraction be 0.5% ethanol BTA (azimidobenzene) soak two hours to keep Cu
2the stability of O.Separately compare test not add NaF solution.
The Cu prepared
2the electromicroscopic photograph of O thin-film material as shown in Figure 8.Similar with illustration 1, can find out add KF in electrolytic solution after, Cu
2the pattern of O film changes the netted of porous into gradually by typical dendroid.Compared with the electromicroscopic photograph in illustration 1, cavernous structure is here finer and close, and aperture is less.We think, the reticulated structure of this porous makes film have larger specific surface area, are conducive to the transfer in body phase of the absorption of visible ray and electric charge.
The direction of the current break that we are opened by pulsed light judges the conduction type of semi-conductor.As shown in Figure 9, in the moment that pulsed light is opened, three Cu
2the electric current of O film sample, to the sudden change of high current direction, creates a positive photoelectric current, shows the character of n-type semiconductor.We judge the Cu of F doping obtained on ITO substrate thus
2o film is N-shaped Cu
2o.Meanwhile, we can see the Cu that F adulterates
2the photoelectric current of O film have also been obtained certain lifting.Subsequently, we are with the Cu of F doping
2o film is assembled into homojunction battery as n-type semiconductor layer, has carried out IV test.As shown in Figure 10, the Photovoltaic measurement data of three homojunction solar cells are shown in Table 2 IV curve.The Photovoltaic measurement data of table 2 embodiment 2 three homojunction solar cells.(Cell01, Cell02, Cell03 correspond respectively to the addition of KF for 0,0.01 and the sample of 0.015mol/L as the homojunction battery of n-type semiconductor layer).With the Cu of F doping
2o film does not have the high 1-4 of doping doubly as the photoelectric transformation efficiency ratio of the homojunction battery of n-type semiconductor layer.
Table 2
Concrete illustration 3: prepare the Cu of F doping as electrolytic solution using propionic acid copper and acetic acid
2o film
Cu
2the preparation of O film carries out in thermostat water bath.(size is 2 × 5cm first to clean FTO glass before preparation
2): use acetone respectively, ethanol and ultrasonic 5 minutes of distilled water immersion, each ultrasonic end all uses distilled water flushing, then drying for standby.The propionic acid copper of preparation 0.08mol/L and the acetic acid mixed solution of 0.1mol/L are as electrolytic solution, and volume is 100mL.Regulate pH by 4mol/L NaOH solution, in this process, ceaselessly stir with magneton, slowly drip alkali lye to the registration of pH meter with glue head dropper simultaneously and be stabilized in about 4.0.Respectively to adding the precursor of 0.01,0.02mol/L NaF as fluorine in electrolytic solution, then electrolytic solution is put into water-bath and be heated to 60 DEG C.Utilize three-electrode system, with the ito glass cleaned up for working electrode, Pt sheet is to electrode, the Ag/AgCl electrode of saturated KCl is reference electrode, constant voltage deposits, constant voltage deposition time institute's biasing is+0.015V (the Ag/AgCl electrode of the saturated KCl of vs.), and depositing time is 30 minutes.After completion of the reaction, take out FTO glass, use distilled water wash.Put into after sample drying massfraction be 1% ethanol BTA (azimidobenzene) soak two hours to keep Cu
2the stability of O.Separately compare test not add NaF solution.
The Cu prepared
2the electromicroscopic photograph of O thin-film material as shown in Figure 11.For the sample not adding NaF, its pattern presents the stone shape without corner angle, different with the dendroid in illustration 1 and 2, and the change of this and substrate and experiment condition has relation.Similar, add NaF in electrolytic solution after, Cu
2the pattern of O film gradually changes the netted of porous into.Can see, the F doped with Cu under this condition
2the reticulated structure of O film (0.02mol/L NaF) is more obvious.We think, the reticulated structure of this porous makes film have larger specific surface area, are conducive to the transfer in body phase of the absorption of visible ray and electric charge.
We judge the conduction type of semi-conductor by Mott-Schottky slope of a curve.In Figure 12 the Mott-Schottky slope of a curve of three samples be all on the occasion of, show that the sample that we prepare is all n-type semiconductor.In addition, the Cu for F doping can be found out by Mott-Schottky slope of a curve size
2the carrier concentration of O sample obtains very large lifting.This is mainly because the Cu of F doping
2in O, F atom substitutes O atom, can provide extra electronics, at the bottom of conduction band, form a shallow donor doping energy level simultaneously.With the Cu of F doping
2o film is assembled into the IV curve of homojunction battery as shown in Figure 13 as n-type semiconductor layer, and Photovoltaic measurement data are shown in Table 3.The Photovoltaic measurement data of table 3 embodiment 3 three homojunction solar cells.(Cell01, Cell02, Cell03 correspond respectively to the addition of NaF for 0,0.01 and the sample of 0.02mol/L as the homojunction battery of n-type semiconductor layer).The Cu adulterated by F
2the efficiency of the homojunction solar cell that O thin film semiconductor is assembled into also is non-doped with Cu
25 times more than of O homojunction solar cell.
Table 3
Concrete illustration 4: prepare the Cu of F doping as electrolytic solution using venus crystals and formic acid
2o film
Cu
2the preparation of O film carries out in thermostat water bath.(size is 2 × 5cm first to clean FTO glass before preparation
2): use acetone respectively, ethanol and ultrasonic 5 minutes of distilled water immersion, each ultrasonic end all uses distilled water flushing, then drying for standby.The venus crystals of preparation 0.1mol/L and the formic acid mixing solutions of 0.05mol/L are as electrolytic solution, and volume is 100mL.Regulate pH by 4mol/L NaOH solution, in this process, ceaselessly stir with magneton, slowly drip alkali lye to the registration of pH meter with glue head dropper simultaneously and be stabilized in about 6.0.Respectively to adding the precursor of 0.025,0.05mol/L NaF as fluorine in electrolytic solution, then electrolytic solution is put into water-bath and be heated to 80 DEG C.Utilize three-electrode system, with the ito glass cleaned up for working electrode, Pt sheet is to electrode, the Ag/AgCl electrode of saturated KCl is reference electrode, constant voltage deposits, constant voltage deposition time institute's biasing is+0.04V (the Ag/AgCl electrode of the saturated KCl of vs.), and depositing time is 20 minutes.After completion of the reaction, take out FTO glass, use distilled water wash.Put into after sample drying massfraction be 1% ethanol BTA (azimidobenzene) soak two hours to keep Cu
2the stability of O.Separately compare test not add NaF solution.
With illustration 1,2 is the same with 3, due to the regulating and controlling effect of F ion, and the Cu of the F doping prepared under this condition
2o film presents the netted pattern of porous.The reticulated structure of this porous makes film have larger specific surface area, is conducive to the transfer in body phase of the absorption of visible ray and electric charge.The Cu of the F doping prepared under photoelectrochemistry test demonstrates this condition
2o film has larger photoelectric current and carrier concentration, and the performance of battery have also been obtained very large lifting.
Claims (8)
1. the preparation method of the N-shaped Red copper oxide semiconductor film of a Fluorin doped, it is characterized in that: the acid solution of preparation bivalent cupric ion salt, the pH value of regulator solution is slightly acidic, makes electrolytic solution, adds the precursor solution of fluorine in the electrolytic solution, then three-electrode system is utilized, with the conductive glass cleaned up for working electrode, Pt sheet is to electrode, and the Ag/AgCl electrode of saturated KCl is reference electrode, constant voltage deposits, and prepares the N-shaped Red copper oxide semiconductor film of Fluorin doped.
2. the preparation method of the N-shaped Red copper oxide semiconductor film of Fluorin doped according to claim 1, it is characterized in that: in the acid solution of described bivalent cupric ion salt, the concentration of bivalent cupric ion salt is 0.005 ~ 0.1M, is 0.01 ~ 0.1M for cushioning the concentration of the acid of bivalent cupric ion salt.
3. the preparation method of the N-shaped Red copper oxide semiconductor film of Fluorin doped according to claim 1, is characterized in that: the concentration of the precursor solution of fluorine used is 0.005 ~ 0.05mol/L.
4. the preparation method of the N-shaped Red copper oxide semiconductor film of Fluorin doped according to claim 1, is characterized in that: described bivalent cupric ion salt can be Tubercuprose, neutralized verdigris, propionic acid copper, for cushioning sour formic acid, the acetic acid of bivalent cupric ion salt; The precursor of fluorine used is NaF or KF.
5. the preparation method of the N-shaped Red copper oxide semiconductor film of Fluorin doped according to claim 1, is characterized in that: after described adjustment, the pH value of solution is between 3 ~ 6.
6. the preparation method of the N-shaped Red copper oxide semiconductor film of Fluorin doped according to claim 1, it is characterized in that: the described conductive glass as substrate is ito glass or FTO glass, conductive glass before the use, use acetone respectively, ethanol and ultrasonic 5 minutes of distilled water immersion, each ultrasonic end all uses distilled water flushing, and final drying is for subsequent use.
7. the preparation method of the N-shaped Red copper oxide semiconductor film of Fluorin doped according to claim 1, it is characterized in that: described constant voltage deposition time institute's biasing is+0.01 ~ 0.042V (the Ag/AgCl electrode of the saturated KCl of vs.), temperature 60 ~ 80 DEG C, depositing time is 20 ~ 60 minutes.
8. the preparation method of the N-shaped Red copper oxide semiconductor film of Fluorin doped according to claim 1, is characterized in that: describedly will deposit Cu
2put into after conductive glass sample drying after O film massfraction be 0.1% ~ 1% ethanol BTA soak two hours to keep Cu
2the stability of O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510288549.XA CN104947165B (en) | 2015-05-29 | 2015-05-29 | A kind of preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510288549.XA CN104947165B (en) | 2015-05-29 | 2015-05-29 | A kind of preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104947165A true CN104947165A (en) | 2015-09-30 |
| CN104947165B CN104947165B (en) | 2017-11-17 |
Family
ID=54162211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510288549.XA Expired - Fee Related CN104947165B (en) | 2015-05-29 | 2015-05-29 | A kind of preparation method of the n-type cuprous oxide semiconductive thin film of Fluorin doped |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104947165B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696047A (en) * | 2016-01-26 | 2016-06-22 | 太原理工大学 | Rapid preparation method for cuprous oxide nano-film |
| CN106129174A (en) * | 2016-07-07 | 2016-11-16 | 深圳大学 | A kind of fluorine doped cuprous oxide film and preparation method thereof |
| CN108796532A (en) * | 2017-05-03 | 2018-11-13 | 天津大学 | Nickel oxide-cuprous oxide homojunction photocathode and preparation method thereof and the application in photocatalysis |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
-
2015
- 2015-05-29 CN CN201510288549.XA patent/CN104947165B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732928A (en) * | 2012-07-18 | 2012-10-17 | 西北工业大学 | Preparation method of cuprous oxide semiconductor film material |
Non-Patent Citations (5)
| Title |
|---|
| QIONG BAI等: "《n-type doping in Cu2O with F, Cl, and Br: A first-principles study》", 《JOURNAL OF APPLIED PHYSICS》 * |
| SHIXIN WU等: "《Electrochemical deposition of Cl-doped n-type Cu2O on reduced grapheme oxide electrodes》", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| XIAOFEI HAN等: "Characterization of Cl-doped n-type Cu2O prepared by electrodeposition", 《THIN SOLID FILMS》 * |
| 胡飞，等: "《Cu2O半导体薄膜在酸性条件下的电化学沉积》", 《功能材料》 * |
| 陈志钢，等: "《溶液温度和衬底对电化学沉积Cu2O薄膜形貌的影响》", 《材料科学与工程学报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105696047A (en) * | 2016-01-26 | 2016-06-22 | 太原理工大学 | Rapid preparation method for cuprous oxide nano-film |
| CN106129174A (en) * | 2016-07-07 | 2016-11-16 | 深圳大学 | A kind of fluorine doped cuprous oxide film and preparation method thereof |
| CN108796532A (en) * | 2017-05-03 | 2018-11-13 | 天津大学 | Nickel oxide-cuprous oxide homojunction photocathode and preparation method thereof and the application in photocatalysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104947165B (en) | 2017-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Luo et al. | Solution transformation of Cu2O into CuInS2 for solar water splitting | |
| Rovelli et al. | Optimization and stabilization of electrodeposited Cu2ZnSnS4 photocathodes for solar water reduction | |
| Zhao et al. | Electrodeposition of photoactive silicon films for low-cost solar cells | |
| Zhou et al. | Copper selenide (Cu 3 Se 2 and Cu 2− x Se) thin films: electrochemical deposition and electrocatalytic application in quantum dot-sensitized solar cells | |
| Kim et al. | Cost-effective and morphology controllable PVP based highly efficient CuS counter electrodes for high-efficiency quantum dot-sensitized solar cells | |
| Ge et al. | Co-electroplated kesterite bifacial thin-film solar cells: A study of sulfurization temperature | |
| CN102610392A (en) | Metal selenide counter-electrode for dye-sensitized solar cell and preparation method of metal selenide counter-electrode | |
| CN102623195A (en) | Method for preparing solar cell through quantum dot and dye synergistic sensitization of TiO2 nanorod array | |
| CN106128772B (en) | A kind of preparation method of vulcanized lead quantum dot photovoltaic battery | |
| CN106328381B (en) | All solid state quantum dot sensitized solar cell of one kind and preparation method thereof | |
| JP2018046196A (en) | Photoelectric conversion device and manufacturing method of photoelectric conversion device | |
| Guo et al. | Electrodeposited CuInSe2 counter electrodes for efficient and stable quantum dot-sensitized solar cells | |
| CN104319298B (en) | Flexible substrate CdTe thin film solaode and preparation method thereof | |
| Esmaeili-Zare et al. | CIS/CdS/ZnO/ZnO: Al modified photocathode for enhanced photoelectrochemical behavior under visible irradiation: Effects of pH and concentration of electrolyte solution | |
| CN104036964B (en) | The electrochemical preparation method of copper sulfide film | |
| CN104947165A (en) | Production method of fluorine-doped n type cuprous oxide semiconductor film | |
| Izaki et al. | Light-Irradiated Electrochemical Direct Construction of Cu2O/CuO Bilayers by Switching Cathodic/Anodic Polarization in Copper (II)–Tartrate Complex Aqueous Solution | |
| Song et al. | Porous Cu2BaSn (S, Se) 4 film as a photocathode using non-toxic solvent and a ball-milling approach | |
| CN102181893A (en) | Method for preparing indium-enriched CuInSe2 membrane by adjusting pH value and electrodepositing | |
| CN100541822C (en) | DSSC of a kind of nano-crystal film and preparation method thereof | |
| CN104141159A (en) | Method for controlling conduction type of cuprous oxide semiconductor based on concentration of surface active agent in electroplating liquid | |
| CN103515106B (en) | A kind of PbS/ITO thin film based photoelectrochemical photovoltaic cells preparation method | |
| CN105140335A (en) | CZTS film preparation method on transparent conductive substrate through one step | |
| CN101252154A (en) | Method for preparing cuprous thiocyanate thin film using triethanolamine complexing water-based galvanic deposit liquid | |
| CN104167294A (en) | In2S3/CuInS2 thin layer sensitization broadband semiconductor photoanode and preparation method for the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171117 Termination date: 20210529 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |