Background technology
Since nineteen ninety Canham (Appl.Phys.Lett., 1990,57:1046) found under the room temperature after the strong visible photoluminescent of porous silicon (PS), the research of porous silicon has evoked researcher's huge interest, even to this day, porous silicon is considered at the integrated (Mater.Res.Soc.Symp.Proc.2004 of photoelectricity, 818:397, Phys.Status Solid B 2004,241:2767), (Science 2002 for transducer, 298:1759) and photovoltaic device (Thin Solid Films 2005,487:170) etc. there are the potentiality of application in the field.
Porous silicon has unique microcellular structure, huge specific area, and very strong adsorption capacity makes it can become the good carrier of organic molecule.Utilizing porous silicon to inlay organic substance, change the photoelectric properties of porous silicon, is a problem that is worth discussion.As template, in it, add organic substance with porous silicon, and this existing research in the world today (Appl.Phys.Lett., 2001,78:4154, J.Appl.Phys., 2000,88:419, Appl.Phys.Lett., 1993:2655).
Ripe silicon technology and good light, heat and the chemical stability of silicon carrier all provide superior condition for porous silicon and organic substance are compound.At present, to porous silicon/organic research concentrate on mostly luminous on, the research of relevant porous silicon/organic substance composite material photovoltaic performance is then seldom.Porous silicon has the big characteristics of specific area as photovoltaic material, can increase the contact area of organic material and inorganic material, improves the diffusivity of charge carrier, and these characteristics all are beneficial to the preparation photovoltaic device.
In the research of current organic/inorganic composite photo voltaic device, generally all be that to select for use p type organic semiconductor and n type inorganic semiconductor to carry out compound, this is generally to be lower than p type organic semi-conductor carrier mobility because of n type organic semi-conductor carrier mobility.N, N '-phenyl-3,4,9,10-perylene tetracarboxylic imidodicarbonic diamide (DPP) they are a kind of n type organic semiconductors, its electron mobility is up to 0.017cm
2/ (Vs) (Chem.Mater., 2007,19:816), can with p type organic semiconductor phthalocyanine [0.02cm commonly used
2/ (Vs)] and thiophene [0.027cm
2/ (Vs)] (Adv.Mater., 2002, hole mobility 14:99) compares favourably.
Summary of the invention
The invention provides the preparation method of simple, the lower porous silicon/DPP photoelectricity composite material of a kind of technology to equipment requirements.
The preparation method of a kind of porous silicon/DPP photoelectricity composite material may further comprise the steps:
(1) monocrystalline silicon piece is cleaned degreasing, and in acetone, ethanol and deionized water, carry out sonicated respectively, oven dry,
Monocrystalline silicon piece is boron doped p type monocrystalline silicon piece, and resistivity is 7.0-7.8 Ω cm.If use the lower silicon chip of resistivity, the bad control of porous silicon pattern that then obtains; If use the higher silicon chip of resistivity, then reaction speed is too slow, influences the efficient of material preparation.
The sonicated time is 10~15 minutes, guarantees to remove impurity such as the dust of monocrystalline silicon surface and grease.
(2) monocrystalline silicon piece of oven dry is removed surperficial SiO with hydrofluoric acid clean
2, the monocrystalline silicon piece back spatter one deck gold film after processing.
Hydrofluoric acid concentration is 5~10%, both can remove SiO
2, do not cause monocrystalline silicon surface to be destroyed again.
The gold film thickness is 30~50nm, and bonding crystal silicon and electrode form good Ohmic contact.
(3) under power on condition, as anode, platinized platinum is inserted and is carried out electrochemical corrosion in the electrolyte as negative electrode with the monocrystalline silicon piece that is covered with golden film.
Electrical current density is 5~10mA/cm
2, electrolyte is the mixed solution of hydrofluoric acid and ethanol, wherein the mass fraction of hydrofluoric acid is 20~25%; The electrochemical corrosion time is 10~60min.
(4) under power on condition, as negative electrode, platinized platinum is inserted in the DPP saturated solution that contains trifluoroacetic acid and is carried out electrochemical deposition as anode with the monocrystalline silicon piece after the corrosion, and vacuumize has deposited the monocrystalline silicon piece of DPP, makes finished product.
The solvent of described DPP saturated solution is N, dinethylformamide (DMF).
The DPP saturated solution that contains trifluoroacetic acid in the said method can prepare by the following method:
(1) with 3,4,9,10-perylene tetracarboxylic dianhydride (PTDA), aniline, acetic anhydride zinc join in the quinoline, mix the back in N
2In 180~185 ℃ of down reactions, the back cold filtration that reacts completely obtains head product;
(2) with head product with NaOH solution boil be washed till cleaning solution and do not have an obvious green till, be washed till neutrality with deionized water again, use absolute ethanol washing at last three times, dry the bronzing solid;
(3) with the vacuum sublimation of bronzing solid, solidify kermesinus acicular crystal product, promptly be pure DPP.
(4) excessive DPP is dissolved among the DMF, splashes into trifluoroacetic acid then, promptly obtain containing the DMF saturated solution of the DPP of trifluoroacetic acid.
Electrical current density is 10~12mA/cm
2, the electrochemical deposition time is 15~30min.
The vacuumize temperature is 110~120 ℃, and the time is 3~5h.
The present invention has made full use of the loose structure and the big advantage of specific area of porous silicon, with it is template, method by electrochemical deposition, in porous silicon, inlay a kind of organic semiconducting materials DPP that has than high electron mobility, realize that both is compound, this complex method technology is simple, and is lower to equipment requirements; In addition because porous silicon and DPP level structure coupling, thus both compound after, be expected to improve the separation of charge efficient of system photoproduction exciton, have the potentiality that obtain application in field of photovoltaic devices.
Embodiment
Contain the preparation of the DPP saturated solution of trifluoroacetic acid
(1) 0.98g (2.5mmol) PTDA, 1.37ml (10mmol) aniline, 0.5g acetic anhydride zinc are joined in the 10ml quinoline, mix the back at N
2In 185 ℃ of reactions 8 hours, cold filtration obtained head product down in protection;
(2) head product is boiled with 5%NaOH solution earlier be washed till cleaning solution and do not have obvious green, be washed till neutrality with deionized water then, use absolute ethanol washing at last three times, dry the bronzing solid;
(3) with the vacuum sublimation of bronzing solid, solidify kermesinus acicular crystal product, promptly be pure DPP, productive rate is 78.2%.
(4) excessive DPP is dissolved in N, in the dinethylformamide (DMF), forms suspension-turbid liquid, splash into the trifluoroacetic acid 0.5ml of 0.1mol/L then, promptly obtain containing the DPP saturated solution of trifluoroacetic acid, its solvent is N, dinethylformamide.
The preparation of porous silicon/DPP photoelectricity composite material
Embodiment 1
1. the monocrystalline silicon piece of boron doped p type (111) is cleaned degreasing, and in acetone, ethanol and deionized water, carried out sonicated respectively 10 minutes, oven dry;
2. the monocrystalline silicon piece of oven dry is removed the SiO on surface with 10% hydrofluoric acid treatment
2, monocrystalline silicon piece back spatter one layer thickness after processing is the golden film of 50nm;
3. under power on condition, as anode, platinized platinum is as negative electrode with the monocrystalline silicon piece that is covered with golden film, inserts in the mixed solution (the quality percentage composition of HF is 20%) of hydrofluoric acid and ethanol and carries out electrochemical corrosion 10 minutes, and wherein electrical current density is 5mA/cm
2
4. under power on condition, as negative electrode, platinized platinum is inserted in the DPP saturated solution that contains trifluoroacetic acid and is carried out electrochemical deposition 15min as anode with the monocrystalline silicon piece after the corrosion, baking has deposited the monocrystalline silicon piece 3h of DPP in 110 ℃ vacuum drying chamber, makes finished product.Wherein electrical current density is 10mA/cm
2
Embodiment 2
1. the monocrystalline silicon piece of boron doped p type (111) is cleaned degreasing, and in acetone, ethanol and deionized water, carried out sonicated respectively 10 minutes, oven dry;
2. the monocrystalline silicon piece of oven dry is removed the SiO on surface with 10% hydrofluoric acid treatment
2, monocrystalline silicon piece back spatter one layer thickness after processing is the golden film of 50nm;
3. under power on condition, as anode, platinized platinum is as negative electrode with the monocrystalline silicon piece that is covered with golden film, inserts in the mixed solution (the quality percentage composition of HF is 20%) of hydrofluoric acid and ethanol and carries out electrochemical corrosion 60 minutes, and wherein electrical current density is 5mA/cm
2
4. under power on condition, as negative electrode, platinized platinum is inserted in the DPP saturated solution that contains trifluoroacetic acid and is carried out electrochemical deposition 15min as anode with the monocrystalline silicon piece after the corrosion, baking has deposited the monocrystalline silicon piece 3h of DPP in 110 ℃ vacuum drying chamber, makes finished product.Wherein electrical current density is 10mA/cm
2
Embodiment 3
1. the monocrystalline silicon piece of boron doped p type (111) is cleaned degreasing, and in acetone, ethanol and deionized water, carried out sonicated respectively 10 minutes, oven dry;
2. the monocrystalline silicon piece of oven dry is removed the SiO on surface with 10% hydrofluoric acid treatment
2, monocrystalline silicon piece back spatter one layer thickness after processing is the golden film of 30nm;
3. under power on condition, as anode, platinized platinum is as negative electrode with the monocrystalline silicon piece that is covered with golden film, inserts in the mixed solution (the quality percentage composition of HF is 25%) of hydrofluoric acid and ethanol and carries out electrochemical corrosion 10 minutes, and wherein electrical current density is 10mA/cm
2
4. under power on condition, as negative electrode, platinized platinum is inserted in the DPP saturated solution that contains trifluoroacetic acid and is carried out electrochemical deposition 15min as anode with the monocrystalline silicon piece after the corrosion, baking has deposited the monocrystalline silicon piece 3h of DPP in 110 ℃ vacuum drying chamber, makes finished product.Wherein electrical current density is 10mA/cm
2
Embodiment 4
1. the monocrystalline silicon piece of boron doped p type (111) is cleaned degreasing, and in acetone, ethanol and deionized water, carried out sonicated respectively 10 minutes, oven dry;
2. the monocrystalline silicon piece of oven dry is removed the SiO on surface with 10% hydrofluoric acid treatment
2, monocrystalline silicon piece back spatter one layer thickness after processing is the golden film of 30nm;
3. under power on condition, as anode, platinized platinum is as negative electrode with the monocrystalline silicon piece that is covered with golden film, inserts in the mixed solution (the quality percentage composition of HF is 25%) of hydrofluoric acid and ethanol and carries out electrochemical corrosion 60 minutes, and wherein electrical current density is 10mA/cm
2
4. under power on condition, as negative electrode, platinized platinum is inserted in the DPP saturated solution that contains trifluoroacetic acid and is carried out electrochemical deposition 30min as anode with the monocrystalline silicon piece after the corrosion, baking has deposited the monocrystalline silicon piece 5h of DPP in 110 ℃ vacuum drying chamber, makes finished product.Wherein electrical current density is 10mA/cm
2
Embodiment 5
1. the monocrystalline silicon piece of boron doped p type (111) is cleaned degreasing, and in acetone, ethanol and deionized water, carried out sonicated respectively 15 minutes, oven dry;
2. the monocrystalline silicon piece of oven dry is removed the SiO on surface with 10% hydrofluoric acid treatment
2, monocrystalline silicon piece back spatter one layer thickness after processing is the golden film of 50nm;
3. under power on condition, as anode, platinized platinum is as negative electrode with the monocrystalline silicon piece that is covered with golden film, inserts in the mixed solution (the quality percentage composition of HF is 25%) of hydrofluoric acid and ethanol and carries out electrochemical corrosion 30 minutes, and wherein electrical current density is 10mA/cm
2
4. under power on condition, as negative electrode, platinized platinum is inserted in the DPP saturated solution that contains trifluoroacetic acid and is carried out electrochemical deposition 30min as anode with the monocrystalline silicon piece after the corrosion, baking has deposited the monocrystalline silicon piece 3h of DPP in 120 ℃ vacuum drying chamber, makes finished product.Wherein electrical current density is 12mA/cm
2
Embodiment 6
1. the monocrystalline silicon piece of boron doped p type (111) is cleaned degreasing, and in acetone, ethanol and deionized water, carried out sonicated respectively 15 minutes, oven dry;
2. the monocrystalline silicon piece of oven dry is removed the SiO on surface with 10% hydrofluoric acid treatment
2, monocrystalline silicon piece back spatter one layer thickness after processing is the golden film of 50nm;
3. under power on condition, as anode, platinized platinum is as negative electrode with the monocrystalline silicon piece that is covered with golden film, inserts in the mixed solution (the quality percentage composition of HF is 25%) of hydrofluoric acid and ethanol and carries out electrochemical corrosion 60 minutes, and wherein electrical current density is 10mA/cm
2
4. under power on condition, as negative electrode, platinized platinum is inserted in the DPP saturated solution that contains trifluoroacetic acid and is carried out electrochemical deposition 30min as anode with the monocrystalline silicon piece after the corrosion, baking has deposited the monocrystalline silicon piece 5h of DPP in 120 ℃ vacuum drying chamber, makes finished product.Wherein electrical current density is 12mA/cm
2