CN102810648A - Electric conducting thin film, preparation method thereof and organic photoelectric device - Google Patents
Electric conducting thin film, preparation method thereof and organic photoelectric device Download PDFInfo
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Abstract
The embodiment of the invention discloses an electric conducting thin film, a preparation method thereof and an organic photoelectric device. The electric conducting thin film comprises an electric conducting thin film body and a halogen compound positioned on the surface of the electric conducting thin film body. The preparation method of the electric conducting thin film comprises the following steps of: providing the electric conducting thin film body; and processing the electric conducting thin film body by adopting an organic or inorganic solution containing halogens so that the a compound containing the halogens is formed on the surface of the electric conducting thin film body. According to the invention, after the electric conducting thin film provided by the invention is applied to the organic photoelectric device, water vapors and oxygen atoms which are contained in the electric conducting thin film and diffused into an organic layer of the organic photoelectric device can be decreased through the existence of the halogen compound positioned on the surface of the electric conducting thin film, and the light transmitting rate of the electric conducting thin film is enhanced through the existence of the halogen compound, thus the photoelectric property of the organic photoelectric device can be finally improved.
Description
Technical field
The present invention relates to the semiconductor device fabrication process technical field, more particularly, relate to a kind of conductive film, conductive film preparation method and organic electro-optic device.
Background technology
The energy is the valuable source that the mankind depend on for existence and development.Along with the exhaustion day by day of global non-renewable energy resources and the significant damage that environment is caused thereof, exploitation cleaning, regenerative resource are to realize the task of top priority of human social.At present; Solar energy is the most potential clean energy resource; Being inexhaustible regenerative resource, therefore, is that the solar cell (electroluminescent device) of electric energy receives increasing attention as important clean energy resource based on photovoltaic effect with solar energy converting.In addition, organic electroluminescence device (OLED) need not backlight, adopts extremely thin coating of organic material and glass substrate, and when electric current passed through, these organic materials will be luminous; And the OLED display screen can do lighter and thinnerly, and visible angle is bigger, and can significantly save electric energy, therefore, in the more and more rare current society of the energy at present, the research of OLED also all the more received vast people's attention.
Organic electroluminescent device and organic electroluminescence device can be referred to as organic electro-optic device.More common organic electro-optic device mainly is based on the sandwich structure of ITO (Indium Tin Oxides, tin indium oxide) conductive film (can also be other metal-oxide film here) at present: ITO layer, luminescent layer or light-absorption layer (conversion layer), metal electrode layer; Wherein, said ITO is a kind of N type indium oxide of a large amount of doped tin.In organic electro-optic device, the ITO layer is not only as the electrode of device, and taken on the bright dipping or the extinction window of device; Therefore; In order to make organic electro-optic device obtain preferable performance, need make the ITO layer when having satisfactory electrical conductivity, can also have higher light transmittance.
After forming ito thin film, also need handle its surface in the prior art and can improve the interfacial characteristics between ITO laminar surface and the carrier blocking layers in the hope of after using it in the organic electro-optic device.Common ito thin film surface treatment method comprises ultrasonic cleaning, uv ozone processing and oxygen plasma treatment etc.Ultrasonic cleaning can be removed the lip-deep polluter of ITO; After adopting uv ozone or oxygen plasma that the ITO surface is handled; ITO surface with higher tin concentration is corroded; And oxygen is provided to the surface, thereby has increased the oxygen concentration on ITO surface, so can improve the work function of ito thin film; Thereby can improve the efficient of hole transport, help improving the photoelectric properties of organic electro-optic device.
But; After adopting uv ozone or oxygen plasma that ito thin film is handled; The oxygen concentration on ITO surface has increased, and this just makes that in organic electro-optic device the oxygen atom on ITO surface is easy to diffuse to the hole and injects organic layer; Make organic substance oxidized, thereby make organic layer lose the characteristic that the hole is injected.In addition; After adopting uv ozone or oxygen plasma that ito thin film is handled; The hydrophilicrty on ITO surface has improved, and when it is exposed in the atmosphere, can adsorb more steam, and then after being applied to organic electro-optic device; Said steam also diffuses to the hole easily and injects organic layer, thereby causes the organic electro-optic device decay very fast.Have again, after employing uv ozone or oxygen plasma are handled ito thin film, can't improve the light transmittance of ito thin film.
Summary of the invention
In view of this; The present invention provides a kind of conductive film, conductive film preparation method and organic electro-optic device; After being applied to conductive film provided by the present invention in the organic electro-optic device; Can reduce the situation that steam and oxygen atom in the conductive film diffuse to organic layer, and this conductive film has higher light transmittance.
For realizing above-mentioned purpose, the present invention provides following technical scheme:
A kind of conductive film, this conductive film comprises:
The conductive film body;
Be positioned at the halogen compounds of said conductive film body surface.
Preferably, in the above-mentioned conductive film, said conductive film body is tin indium oxide, indium zinc oxide or zinc oxide aluminum.
Preferably, in the above-mentioned conductive film, said conductive film body is a tin indium oxide.
Preferably; In the above-mentioned conductive film; Said halogen compounds is the halogen compounds that halogen atom and at least a atom in the indium in the tin indium oxide, tin and the oxygen in the halogen-containing organic or inorganic solution reacts and form; Perhaps, said halogen compounds is a formed halogen compounds in the halogen-containing organic or inorganic solution.
The present invention also provides a kind of conductive film preparation method, and this method comprises:
The conductive film body is provided;
Adopt halogen-containing organic or inorganic solution that said conductive film body is handled, make to form halogen-containing compound at said conductive film body surface.
Preferably, in the said method, said halogen-containing organic solution is chloroform, chlorobenzene, dichloro-benzenes, carrene, 1,1-dichloroethanes, carbon tetrachloride, 1,1,1-trichloroethanes, 1, the combination of one or more in 2-dichloroethanes and the trichloroethylene.
Preferably, in the said method, said halogen-containing inorganic solution is one or more the combination in hydrofluoric acid, hydrochloric acid, hydrobromic acid and the hydroiodic acid.
The present invention also provides a kind of organic electro-optic device, and this organic electro-optic device comprises: substrate, anode, hole transmission layer, electron transfer layer and negative electrode; Wherein, said male or female comprises conductive film provided by the present invention.
Preferably, said organic electro-optic device is an electroluminescent device, and this electroluminescent device also comprises: hole injection layer and emission layer.
Preferably, said organic electro-optic device is the electroluminescent device, and this electroluminescent device also comprises: collecting layer, hole and absorbed layer.
Can find out that from technique scheme conductive film provided by the present invention comprises: the conductive film body is positioned at the halogen compounds of said conductive film body surface; Conductive film preparation method provided by the present invention comprises: the conductive film body is provided, adopts halogen-containing organic or inorganic solution that said conductive film body is handled, make to form halogen-containing compound at said conductive film body surface.Conductive film provided by the present invention, in being applied to organic electro-optic device after, on the one hand, because its surface is halogen compounds, therefore, the surperficial oxygen concentration of conductive film is lower, is unfavorable for the diffusion of oxygen atom to organic layer; On the other hand, said halogen compounds can stop the oxygen atom in the conductive film to diffuse into organic layer, thereby has avoided the diffusion of oxygen atom to organic layer.In addition; Conductive film provided by the present invention, its surperficial halogen compounds can improve the contact angle on conductive film surface, and the hydrophobicity of conductive film is improved; Thereby after in being applied to organic electro-optic device, be unfavorable for that steam diffuses in the organic layer.Have, conductive film provided by the present invention also can improve its light transmittance again.
Description of drawings
In order to be illustrated more clearly in the embodiment of the invention or technical scheme of the prior art; To do to introduce simply to the accompanying drawing of required use in embodiment or the description of the Prior Art below; Obviously, the accompanying drawing in describing below only is some embodiments of the present invention, for those of ordinary skills; Under the prerequisite of not paying creative work, can also obtain other accompanying drawing according to these accompanying drawings.
Fig. 1 is a kind of conductive film preparation method's that the embodiment of the invention provided schematic flow sheet;
Fig. 2 is the x-ray photoelectron spectrum curve figure on the ito thin film surface that the embodiment of the invention provided;
Fig. 3 is the transmittance graph figure of the ito thin film that the embodiment of the invention provided;
Fig. 4 is the work function curve chart of the ito thin film that the embodiment of the invention provided;
Fig. 5 is the structural representation of a kind of organic electroluminescence device that the embodiment of the invention provided;
Fig. 6 is the structural representation of the another kind of organic electroluminescence device that the embodiment of the invention provided;
Fig. 7 is the structural representation of a kind of organic electroluminescent device that the embodiment of the invention provided;
Fig. 8 is the structural representation of another kind of organic electroluminescent device that the embodiment of the invention provided;
Fig. 9 for the embodiment of the invention provided first, the I-V curve chart of second, the 3rd and the 4th organic electroluminescent device;
Figure 10 is the I-V curve chart of second, the 4th and the 5th organic electroluminescent device that the embodiment of the invention provided.
Embodiment
For make above-mentioned purpose of the present invention, feature and advantage can be more obviously understandable, does detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
A lot of details have been set forth in the following description so that make much of the present invention; But the present invention can also adopt other to be different from alternate manner described here and implement; Those skilled in the art can do similar popularization under the situation of intension of the present invention, so the present invention does not receive the restriction of following disclosed specific embodiment.
The embodiment of the invention discloses a kind of conductive film, this conductive film comprises: the conductive film body; Be positioned at the halogen compounds of said conductive film body surface.
Said conductive film body is generally transparent oxide, for example, can be tin indium oxide (ITO), indium zinc oxide (IZO) or zinc oxide aluminum (AZO) etc.
Be positioned at the halogen compounds of said conductive film body surface, generally form by the said conductive film body of halogen-containing organic or inorganic solution soaking.For example; When said conductive film is ITO; The halogen compounds that said halogen compounds can react and form for the halogen atom in the halogen-containing organic or inorganic solution and at least a atom among the In among the ITO, Sn and the O; Perhaps, said halogen compounds can be formed halogen compounds in the halogen-containing organic or inorganic solution.
Said halogen-containing organic solution can be chloroform, chlorobenzene, dichloro-benzenes, carrene, 1,1-dichloroethanes, carbon tetrachloride, 1,1,1-trichloroethanes, 1, the combination of one or more in 2-dichloroethanes and the trichloroethylene.Said halogen-containing inorganic solution can be one or more the combination in hydrofluoric acid, hydrochloric acid, hydrobromic acid and the hydroiodic acid.
By on can know; Conductive film provided by the present invention comprises: conductive film body and the halogen compounds that is positioned at said conductive film body surface; The existence of said halogen compounds can reduce the oxygen concentration of conductive film body surface; And said halogen compounds can stop oxygen atom in the conductive film body to outdiffusion; And then after being applied to this conductive film in the organic electro-optic device, the oxygen atom in the conductive film is difficult for to the organic layer diffusion, thereby has avoided organic substance oxidized and cause organic layer to lose the characteristic that the hole is injected.
In addition; Conductive film provided by the present invention; Its surperficial halogen compounds can improve the contact angle on conductive film surface, and the hydrophobicity of conductive film is improved, thereby after in being applied to organic electro-optic device; Be unfavorable for that steam diffuses in the organic layer, avoided organic electro-optic device to be in the more atmosphere environment of steam and cause the problem of the lost of life.
Have again; Conductive film provided by the present invention is compared in the prior art conductive film that relies on after uv ozone or the oxygen plasma treatment, has higher light transmittance; After this just makes that this conductive film is applied in the organic electro-optic device, can improve the photoelectric properties of device effectively.
The present invention also provides a kind of conductive film preparation method.With reference to figure 1, conductive film preparation method provided by the present invention specifically comprises the steps:
Step S1: the conductive film body is provided.
Said conductive film body is a transparent oxide, for example, can be tin indium oxide (ITO), indium zinc oxide (IZO) or zinc oxide aluminum (AZO) etc.Said conductive film body generally is to use as electrode in organic electro-optic device; Therefore; The carrier of this conductive film body can be glass; That is: said conductive film body is coated on glass, need conductive film body and said glass carrier be done as a whole the processing in the subsequent technique.
Step S2: adopt halogen-containing organic or inorganic solution that said conductive film body is handled, make to form halogen-containing compound at said conductive film body surface.
Before the halogen-containing organic or inorganic solution of employing is handled said conductive film body; At first the conductive film body is carried out preliminary treatment; Detailed process is: the glass that will be coated with the conductive film body is put into ultrasonic water bath; Utilize acetone, absolute ethyl alcohol and deionized water said conductive film body respectively to be cleaned 20 minutes respectively, then it is taken out from ultrasonic water bath and dries as solvent.
The conductive film body is carried out the conductive film body being put into halogen-containing organic or inorganic solution together with its glass carrier after the preliminary treatment.Halogen-containing organic solution described in the embodiment of the invention can be chloroform, chlorobenzene, dichloro-benzenes, carrene, 1; 1-dichloroethanes, carbon tetrachloride, 1; 1; 1-trichloroethanes, 1, the combination of one or more in 2-dichloroethanes and the trichloroethylene, said halogen-containing inorganic solution can be one or more the combination in hydrofluoric acid, hydrochloric acid, hydrobromic acid and the hydroiodic acid.
After said conductive film body soaks in halogen-containing organic or inorganic solution; Because the polarization of organic solvent in the solution, the halogen atom in the solution are prone to discharge and react with the atom of conductive film body surface and to form halogen-containing compound.For example, for ITO conductive film body, form halogen-containing compound on the ITO surface thereby halogen atom in the solution and ITO be lip-deep In, a kind of atom among Sn and the O or multiple atom react.In addition, some halogen-containing compounds of spontaneous formation also possibly be deposited on the surface of conductive film body in the halogen-containing organic or inorganic solution.
In the technical process that adopts halogen-containing organic or inorganic solution that said conductive film body is soaked, the amount that can change has: polarity of solvent and soak time etc. in the content of halogen, the solution in the solution; Particularly, the content of halogen can realize that polarity of solvent can realize that soak time can artificially be controlled through selecting different solvents for use through the ratio of regulating solute and solvent.
Choose four identical ITO conductive film body samples in the present embodiment; Make three samples wherein in identical halogen-containing solution (for example being chloride solution), carry out immersion treatment; And the time of three sample immersions is respectively 20min, 40min and 60min; Then three ITO and untreated ITO after the immersion treatment are tested respectively, the gained related data sees also Fig. 2, Fig. 3 and Fig. 4.
With reference to figure 2; Fig. 2 is x-ray photoelectron power spectrum (XPS) curve chart on ito thin film provided by the present invention surface; Show the XPS curve of above-mentioned four ito thin films among the figure respectively, can find out by figure, after chloride solution carries out immersion treatment to ito thin film; The 2p characteristic peak of chlorine can be seen in the ITO surface in the binding energy (Binding energy) of 195～205eV, do not have the ITO surface of immersion treatment then not have the 2p characteristic peak of chlorine.
With reference to figure 3; Fig. 3 is the transmittance graph figure of ito thin film provided by the present invention; Show the transmittance graph of above-mentioned four ito thin films among the figure respectively, can find out by figure, in visible-range; Soak time is that the ito thin film of 60min is compared other three ito thin films, and its transmissivity has obviously improved.Soak time is longer, then means in the halogen concentration on ito thin film surface higherly, and higher halogen concentration can improve the transmissivity of ito thin film, thereby after being applied in the organic electro-optic device, can improve the light transmittance of device.
Need to prove; Adopt the prepared conductive film that comes out of method provided by the present invention, its transmissivity (or claiming light transmittance) has improved, but its electric conductivity does not reduce; That is: conductive film provided by the present invention can improve its transmissivity when guaranteeing its electric conductivity.
With reference to figure 4, Fig. 4 is the work function curve chart of ito thin film provided by the present invention, shows the work function curve of above-mentioned four ito thin films among the figure respectively; Can find out by figure, the ito thin film after halogen-containing solution-treated, its work function (being binding energy) has obviously improved; And soak time is long more; Its corresponding work function improves greatly more, thereby after being applied to the ito thin film after the immersion treatment in the organic electro-optic device, can be beneficial to the injection of device holes.
By on can know; Conductive film preparation method provided by the present invention; Through adopting halogen-containing organic or inorganic solution that the conductive film body is carried out immersion treatment; Thereby formed halogen-containing compound at the conductive film body surface, said conductive film body and said halogen compounds have constituted conductive film jointly.After being applied to this conductive film in the organic electro-optic device; The halogen compounds on conductive film surface not only can avoid steam and oxygen atom to be diffused in the organic layer of device, and; The existence of said halogen compounds can improve the contact angle on conductive film surface; Increase the work function of conductive film, and make the transmissivity of conductive film improve, thereby be beneficial to the light transmission of improving organic electro-optic device.
In addition, the preparation method of conductive film provided by the present invention only need make conductive film body immersion treatment in halogen-containing organic or inorganic solution get final product; Compare in the prior art and to rely on uv ozone that conductive film is handled, the present invention has following advantage: rely on uv ozone to handle, need expensive large-scale instrument; And complicated operation; The present invention need not large-scale expensive instrument, escapable cost, and simple to operate; Rely on uv ozone to handle, need use the Hg metal, and the use meeting of Hg causes serious hidden danger to the environment and the mankind, only need among the present invention to use halogen-containing organic or inorganic solution, therefore, can avoid heavy metal Hg that the mankind are worked the mischief.
Except foregoing description, the present invention also provides a kind of organic electro-optic device, and said organic electro-optic device can be organic electroluminescence device, also can be organic electroluminescent device.Introduce the structure of organic electroluminescence device and organic electroluminescent device respectively below in conjunction with accompanying drawing.
With reference to figure 5; Fig. 5 is the structural representation of a kind of organic electroluminescence device that the embodiment of the invention provided, and this organic electroluminescence device specifically comprises: substrate 1 (can be glass), anode 2, hole injection layer 3, hole transmission layer 4, reflector 5, electron transfer layer 6 and negative electrode 7 that order is provided with; Wherein, said anode 2 and negative electrode 7 are connected the positive pole and the negative pole of power supply respectively.
With reference to figure 6; Fig. 6 is the structural representation of the another kind of organic electroluminescence device that the embodiment of the invention provided, and this schemes relative Fig. 5, between anode 2 and hole injection layer 3, has increased hole tunnel layer (or resilient coating) 10; Other structure is all same as shown in Figure 5, repeats no more at this.The effect of Fig. 6 holes tunnel layer 10 mainly is: reduce the potential barrier between anode 2 and the hole injection layer 3, improve the transmission and the collection efficiency in hole, thereby improve the performance of device.
In the embodiment of the invention, the organic electroluminescence device of corresponding which kind of structure no matter, the anode on it is conductive film provided by the present invention.In organic electroluminescence device, use conductive film provided by the present invention as anode, when guaranteeing the electric conductivity of this device, can also improve the light transmittance of device.
Certainly, also can be through being provided with so that the negative electrode of organic electroluminescence device is a conductive film provided by the present invention.
With reference to figure 7 and Fig. 8; Fig. 7 and Fig. 8 show the structural representation of two kinds of different organic electroluminescent devices respectively, and the structure of organic electroluminescent device specifically comprises shown in Fig. 7: the substrate 1 (can be glass) that order is provided with, anode 2, collecting layer, hole 8, hole transmission layer 4, absorbed layer (or claiming conversion layer) 11, electron transfer layer 6 and negative electrode 7; Wherein, said anode 2 and negative electrode 7 are connected the positive terminal and the negative terminal of voltmeter respectively.The difference of Fig. 8 and Fig. 7 is: between anode 2 and collecting layer, hole 8, increased hole tunnel layer (or resilient coating) 10 among Fig. 8, the effect of this hole tunnel layer 10 is identical with the effect of Fig. 6 holes tunnel layer 10.
Similar with organic electroluminescence device, organic electroluminescent device provided by the present invention, the anode on it also are conductive film provided by the present invention.In organic electroluminescent device, use conductive film provided by the present invention as anode, the short circuit current of device and photoelectric conversion efficiency all are improved.Introduce the main manufacturing process of organic electroluminescent device as shown in Figure 7 provided by the present invention below in detail with a specific embodiment, specific as follows:
The first, the preparation of anode
Adopt the anode of ito thin film as organic electroluminescent device in the present embodiment, the concrete manufacture method of said ito thin film is: at first ito thin film is coated on the glass substrate; The glass substrate that will be coated with ito thin film is then put into ultrasonic water bath, utilize respectively acetone, absolute ethyl alcohol and deionized water as solvent to each ultrasonic cleaning 20min of said ito thin film; Dry afterwards this glass substrate and on ito thin film; Then the said glass substrate that is coated with ito thin film is put into the beaker that fills chloroform, make said ito thin film in the solution of chloroform, soak 20min, formed halogen-containing compound on the surface of ito thin film through ultrasonic mode; With high-purity nitrogen the ito thin film on the glass substrate is dried up at last.
The second, the preparation of collecting layer, hole
The glass substrate that is coated with ito thin film is positioned on the sucker of spin coating appearance; Spin coating one strata 3 on said ito thin film then; 4-ethene dioxythiophene: the aqueous solution of p-methyl benzenesulfonic acid (PEDOT:PSS); In air, it is heated to 140 ℃ afterwards, and keeps 40min, thereby on ito thin film, formed the collecting layer, hole.
When collecting layer, spin coating hole, the may command spin speed is 4000r/min, and the spin coating time is 60s.
Three, the preparation of absorbed layer
The glass substrate that will be formed with the collecting layer, hole is put into the glove box that is full of nitrogen; The mixed solution of the derivative (PCBM) of spin coating one strata 3-hexyl thiophene (P3HT) and fullerene on collecting layer, said hole; In glove box, it is heated to 120 ℃ afterwards; And keep 10min, finally on collecting layer, said hole, formed absorbed layer.
When the spin coating absorbed layer, the may command spin speed is 2000r/min, and the spin coating time is 60s.
Need to prove that the P3HT described in the present embodiment in the absorbed layer has the function of hole transport simultaneously, therefore, has saved hole transmission layer in this organic electroluminescent device.
Four, the preparation of electron transfer layer
Depositing fluorinated lithium (LiF) is as electron transfer layer on said absorbed layer, and the deposition velocity of may command LiF is 0.01nm/sec in the concrete deposition process, and deposition process carries out in vacuum chamber, and the vacuum degree of vacuum chamber can be controlled between 5E-7～9E-7Torr.
Five, the preparation of negative electrode
On electron transfer layer, deposit the thick aluminium (Al) of 100nm, thereby form the negative electrode of organic electroluminescent device.The deposition velocity of Al is 0.2nm/sec in the concrete deposition process, and deposition process carries out in vacuum chamber, and the vacuum degree of vacuum chamber can be controlled between 5E-7～9E-7Torr.
So far, first organic electroluminescent element manufacturing finishes.Afterwards, make all the other four organic electroluminescent devices according to above-mentioned steps again, four organic electroluminescent devices of this of follow-up making and first difference are respectively:
Second organic electroluminescent device: in the preparation process of anode, make ito thin film in chloroform soln, soak 40min, other Step By Conditions are all identical with first;
The 3rd organic electroluminescent device: in the preparation process of anode, make ito thin film in chloroform soln, soak 60min, other Step By Conditions are all identical with first;
The 4th organic electroluminescent device: in the preparation process of anode; Only utilize acetone, absolute ethyl alcohol and deionized water as solvent to each ultrasonic cleaning 20min of ito thin film; Do not adopt chloroform soln to soak said ito thin film, other Step By Conditions are all identical with first;
The 5th organic electroluminescent device: in the preparation process of anode; Utilize acetone, absolute ethyl alcohol and deionized water as solvent to each ultrasonic cleaning 20min of ito thin film after; Adopt uv ozone that said ito thin film is handled 15min; Do not adopt chloroform soln to soak said ito thin film, other Step By Conditions are all identical with first.
After above-mentioned five organic electroluminescent element manufacturing are accomplished, these five organic electroluminescent devices are carried out electric performance test, test result is as shown in the table:
Can know by last table; In contrast to the 4th the organic electroluminescent device that only cleans ito thin film and form and the 5th organic electroluminescent device that the ito thin film cleaning is formed after uv ozone is handled; Second organic electroluminescent device makes ito thin film in chloroform soln, soak 40min in forming process; Therefore, it has shown open circuit voltage, short-circuit current density and higher photoelectric conversion efficiency preferably.In addition; The 4th organic electroluminescent device and first, second and the 3rd organic electroluminescent device are compared; Owing to the ito thin film in the 4th organic electroluminescent device only cleans; And first, the ito thin film in second and the 3rd the organic electroluminescent device all soaks in chloroform soln; Though the asynchronism(-nization) of soaking,, these three organic electroluminescent devices have all shown open circuit voltage, short circuit current, fill factor, curve factor and photoelectric conversion efficiency preferably.
Therefore; In contrast to only ito thin film is cleaned or cleaning after uv ozone is handled the final organic electroluminescent device that forms; Ito thin film is soaked in chloroform behind the appropriate time and the organic electroluminescent device that forms, and the latter has higher open circuit voltage, short-circuit current density, fill factor, curve factor and photoelectric conversion efficiency.
With reference to figure 9; Fig. 9 be above-mentioned first, the I-V curve chart of second, the 3rd and the 4th organic electroluminescent device; Show these four organic electroluminescent devices among the figure respectively under dark current and the I-V curve chart under the situation of illumination is being arranged, therefore, 8 curves are arranged in the corresponding diagram 9.By figure can know, when these four organic electroluminescent devices in the following time of situation of dark current, it does not almost all produce voltage; In the time of illumination, all can produce voltage on it, for the 4th organic electroluminescent device; Ito thin film by on it only cleans, and therefore, the voltage that it produced is minimum; First that forms for making ito thin film soak 20min and 40min respectively and second organic electroluminescent device, the voltage that it produced is bigger.
With reference to Figure 10; Figure 10 is the I-V curve chart of above-mentioned second, the 4th and the 5th organic electroluminescent device; Show these three organic electroluminescent devices among the figure respectively under dark current and the I-V curve chart under the situation of illumination is being arranged, therefore, 6 curves are arranged among corresponding Figure 10.By figure can know, when these three organic electroluminescent devices in the following time of situation of dark current, it does not almost all produce voltage; In the time of illumination, all can produce voltage on it, and for the 4th organic electroluminescent device; Ito thin film by on it only cleans, and therefore, the voltage that it produced is minimum; For the 5th organic electroluminescent device, the ito thin film on it is cleaning after uv ozone is handled, therefore; The voltage that the voltage that it produced is produced greater than the 4th organic electroluminescent device, still, the voltage that the voltage that it produced is produced less than second organic electroluminescent device.Second organic electroluminescent device, the ito thin film on it has soaked 40min in chloroform soln, and its voltage that under light conditions, is produced is maximum.
By on can know; Organic electro-optic device provided by the present invention, the conductive film that is adopted by on it male or female carries out immersion treatment through halogen-containing organic or inorganic solution to be crossed, therefore; Formed halogen-containing compound on the conductive film surface; The existence of said halogen-containing compound can reduce that steam and oxygen atom diffuse in the organic layer of device in the conductive film, and can improve the contact angle of conductive film, increases the work function of conductive film; Increase the light transmittance of conductive film, these can both improve the photoelectric properties of device effectively.
Conductive film provided by the present invention, conductive film preparation method and organic electro-optic device, the described emphasis of each several part is different, the reference each other of relevant part.
Need to prove; In this article; Relational terms such as first and second grades only is used for an entity or operation are made a distinction with another entity or operation, and not necessarily requires or hint relation or the order that has any this reality between these entities or the operation.And; Term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability; Thereby make and comprise that process, method, article or the equipment of a series of key elements not only comprise those key elements; But also comprise other key elements of clearly not listing, or also be included as this process, method, article or equipment intrinsic key element.Under the situation that do not having much more more restrictions, the key element that limits by statement " comprising ... ", and be not precluded within process, method, article or the equipment that comprises said key element and also have other identical element.
To the above-mentioned explanation of the disclosed embodiments, make this area professional and technical personnel can realize or use the present invention.Multiple modification to these embodiment will be conspicuous concerning those skilled in the art, and defined General Principle can realize under the situation that does not break away from the spirit or scope of the present invention in other embodiments among this paper.Therefore, the present invention will can not be restricted to these embodiment shown in this paper, but will meet and principle disclosed herein and features of novelty the wideest corresponding to scope.
Claims (10)
1. a conductive film is characterized in that, comprising:
The conductive film body;
Be positioned at the halogen compounds of said conductive film body surface.
2. conductive film according to claim 1 is characterized in that, said conductive film body is tin indium oxide, indium zinc oxide or zinc oxide aluminum.
3. conductive film according to claim 2 is characterized in that, said conductive film body is a tin indium oxide.
4. conductive film according to claim 3; It is characterized in that; Said halogen compounds is the halogen compounds that halogen atom and at least a atom in the indium in the tin indium oxide, tin and the oxygen in the halogen-containing organic or inorganic solution reacts and form; Perhaps, said halogen compounds is a formed halogen compounds in the halogen-containing organic or inorganic solution.
5. a conductive film preparation method is characterized in that, comprising:
The conductive film body is provided;
Adopt halogen-containing organic or inorganic solution that said conductive film body is handled, make to form halogen-containing compound at said conductive film body surface.
6. method according to claim 5 is characterized in that, said halogen-containing organic solution is chloroform, chlorobenzene, dichloro-benzenes, carrene, 1; 1-dichloroethanes, carbon tetrachloride, 1; 1,1-trichloroethanes, 1, the combination of one or more in 2-dichloroethanes and the trichloroethylene.
7. method according to claim 5 is characterized in that, said halogen-containing inorganic solution is one or more the combination in hydrofluoric acid, hydrochloric acid, hydrobromic acid and the hydroiodic acid.
8. an organic electro-optic device is characterized in that, comprising: substrate, anode, hole transmission layer, electron transfer layer and negative electrode; Wherein, said male or female comprises like each described conductive film of claim 1～4.
9. organic electro-optic device according to claim 8 is characterized in that, said organic electro-optic device is an electroluminescent device, and this electroluminescent device also comprises: hole injection layer and emission layer.
10. organic electro-optic device according to claim 8 is characterized in that, said organic electro-optic device is the electroluminescent device, and this electroluminescent device also comprises: collecting layer, hole and absorbed layer.
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