CN102348777A - Method of depositing amorphous hydrocarbon nitride (a-CN:Hx) film, organic EL device, and process for producing same - Google Patents

Method of depositing amorphous hydrocarbon nitride (a-CN:Hx) film, organic EL device, and process for producing same Download PDF

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CN102348777A
CN102348777A CN2010800118272A CN201080011827A CN102348777A CN 102348777 A CN102348777 A CN 102348777A CN 2010800118272 A CN2010800118272 A CN 2010800118272A CN 201080011827 A CN201080011827 A CN 201080011827A CN 102348777 A CN102348777 A CN 102348777A
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film
gas
layer
plasma
nitride
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石川拓
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Tokyo Electron Ltd
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass

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Abstract

A method in which a high-density plasma having a relatively low electron temperature is used to stably form an a-CN:Hx film containing carbon-nitrogen (C-N) bonds and having few defects and satisfactory properties using, as a feed gas, a hydrocarbon compound containing a carbon-nitrogen (C-N) bond. Provided is an organic device including an a-CN:Hx film. A hydrocarbon compound containing a C-N bond and either nitrogen or ammonia are used as feed gases to deposit a luminescent layer. A hole injection/transportation layer is formed on the underside of the luminescent layer, and an electron injection layer is formed on the upperside of the luminescent layer. Thus, an organic device including an amorphous hydrocarbon nitride (a-CN:Hx) film as the luminescent layer is obtained.

Description

Amorphous hydrocarbon nitride (a-CN:H x) film, organic EL device and the method for manufacture thereof of film
Technical field
For example the present invention relates to amorphous hydrocarbon nitride (amorphous hydrocarbon nitride, a-CN:H that the luminescent layer as organic EL device uses x) film film, used this amorphous hydrocarbon nitride (a-CN:H x) organic EL device and the method for manufacture thereof of film.
Background technology
In recent years, utilize the use organic compound and the OLED display of its luminous organic electroluminescent (EL:Electro Luminescence) element is received much concern.Because organic EL has characteristics such as luminous, speed of response is fast, consumes electric power is low, therefore do not need backlight, can expect the application in the display part of for example portable machine etc.
Studied various compound-materials as the luminescent layer of organic EL, as one of thin-film light emitting device reported the amorphous hydrocarbon nitride film (below, be called a-CN:H xFilm) (for example, with reference to non-patent literature 1).In addition, according to non-patent literature 2, through using a-CN:H xFilm can send red, green, blue three coloured light as luminescent layer, can think the light that sends whole colors through these three primary colors.In addition, in non-patent literature 1,, use methane (CH as material gas through the plasma CVD equipment of parallel plate-type RF magnetron discharge mode 4) gas and nitrogen (N 2) formation a-CN:H xFilm.
Non-patent literature 1: " stopping up of high frequency プ ラ ズ マ プ ロ セ ス To I Ru function thing forming thin film と そ ying is used " clarified butter is good bright, Tokyo motor university, 2005
Non-patent literature 2: " Studyof Amorphous Carbon Nitride Films Aiming at White Light Emitting Devices ", Kunio Itoh and Yuta lwano, mountain, Tianjin high commissioner summary, No. 49,2007
Summary of the invention
Invent problem to be solved
Yet, the a-CN:H of the plasma CVD equipment of the parallel plate-type RF magnetic charging mode of record in utilizing above-mentioned non-patent literature 1 xIn the film forming of film; In order to make nitrogen activation as material gas; Form carbon-nitrogen bond, carry out film forming, the problem that therefore exists the film itself that forms to sustain damage owing to use by the maximum high plasma body that produces to the high magnetic charging of 10eV of the electronic temp in the plasma body.And, in plasma body, make methane gas (CH as material gas 4) and nitrogen (N 2) reaction bonded, therefore, the a-CN:H that is forming xThe stability of the carbon-nitrogen in the film (C-N) alkali fluctuates, and produces dangling bonds in the film, so there is a-CN:H xThe problem of the deterioration in characteristics of film.
Therefore; The object of the present invention is to provide through using the method for the lower high density plasma of electronic temp;, form and stably contain (C-N) key, defective is few, characteristic is good a-CN:H as material gas with the hydrocarbon polymer that contains carbon-nitrogen (C-N) key xThe film of film.In addition, be to provide use this a-CN:H xThe organic assembly of film and method of manufacture thereof.
Be used to solve the method for problem
According to the present invention, a kind of amorphous hydrocarbon nitride (a-CN:H that uses as the luminescent layer of organic assembly is provided x) film of film, comprising: in processing vessel, supply with the operation of plasma exciatiaon with gas, the hydrocarbon gas that contains the C-N key and nitrogen or ammonia as material gas; With produce the plasma body of above-mentioned plasma exciatiaon with gas through microwave, make the operation of above-mentioned materials gas activation through this plasma body.
According to such film,, therefore in plasma body, need not make CH at the high-energy excited state owing to use the gas that has contained the C-N key in the stage of material gas 4And N 2Reaction forms the C-N key, can be contained stably that C-N key, defective are few, the amorphous hydrocarbon nitride (a-CN:H of excellent in luminous characteristics x) film.
In addition; According to the present invention, a kind of method of manufacture of organic assembly is provided, wherein from another viewpoint; On the handled object that is formed with the 1st conductive electrode, form the hole and inject transfer layer, inject the amorphous hydrocarbon nitride (a-CN:H of transfer layer superimposed layer luminescent layer in above-mentioned hole x) film, at above-mentioned amorphous hydrocarbon nitride (a-CN:H x) film superimposed layer electron injecting layer, at above-mentioned electron injecting layer superimposed layer the 2nd conductive electrode, lamination is to cover above-mentioned handled object, the 1st conductive electrode, above-mentioned hole injection transfer layer, above-mentioned amorphous hydrocarbon nitride (a-CN:H x) sealing membrane that seals of the mode of film, above-mentioned electron injecting layer, above-mentioned the 2nd conductive electrode.
In addition; According to the present invention from another viewpoint; A kind of organic assembly is provided, and it possesses the hole that on the handled object that is formed with the 1st conductive electrode, forms and injects transfer layer, injects the amorphous hydrocarbon nitride (a-CN:H of the luminescent layer of transfer layer superimposed layer in above-mentioned hole x) film, at above-mentioned amorphous hydrocarbon nitride (a-CN:H x) electron injecting layer of film superimposed layer, inject transfer layer, above-mentioned amorphous hydrocarbon nitride (a-CN:H at the 2nd conductive electrode of above-mentioned electron injecting layer superimposed layer with to cover above-mentioned handled object, above-mentioned the 1st conductive electrode, above-mentioned hole x) sealing membrane that seals of the mode of film, above-mentioned electron injecting layer, above-mentioned the 2nd conductive electrode.
The effect of invention
According to the present invention; Through using the method for the lower high density plasma of electronic temp;, realized forming and stably contained carbon-nitrogen (C-N) key, defective is few, characteristic is good a-CN:H as material gas with the hydrocarbon gas that contains carbon-nitrogen (C-N) key xThe film of film also provides and has used this a-CN:H xThe organic assembly of film and method of manufacture thereof.
Description of drawings
Fig. 1 is the explanatory view of the manufacturing process of the relevant organic assembly of expression embodiment of the present invention.
Fig. 2 is the explanatory view of the relevant base plate processing system of embodiment of the present invention.
Fig. 3 is the schematic explanatory view of the present invention's vapor deposition treatment device 30 of being correlated with.
Fig. 4 is the explanatory view of the relevant RLSA type plasma processing apparatus of embodiment of the present invention.
Fig. 5 is the explanatory view of the relevant RLSA type microwave plasma processing apparatus PM2 ' of other embodiment of the present invention.
Nomenclature
1 ... Substrate board treatment
10 ... The 1st conductive electrode
11 ... Transfer layer is injected in the hole
12 ... Luminescent layer (a-CN:H xFilm)
13 ... Electron injecting layer
14 ... The 2nd conductive electrode
15 ... Sealing membrane
20 ... Control device
30 ... The vapor deposition treatment device
Embodiment
Below, with reference to description of drawings embodiment of the present invention.In addition, in this specification sheets and accompanying drawing, to having the integrant that identical function constitutes in fact, the symbol identical through mark omits repeat specification.
At first, to the method for manufacture of the relevant organic assembly of embodiment of the present invention, describe with reference to the Fig. 1 that representes its schematic configuration.
(method of manufacture of organic assembly)
Shown in Fig. 1 (a), for example on glass substrate G, be pre-formed the 1st conductive electrode (anode) 10 that constitute by indium tin oxide (ITO:Indium Tin Oxide) as anode layer.Cleaning should the surface after, transfer layer 11 is injected in the hole that on the 1st conductive electrode 10, forms the organic compound of CuPe for example etc. through vapor deposition.
Then; Shown in Fig. 1 (b); Use nitrogenous hydrocarbon gas and nitrogen or ammonia as material gas; Or use the hydrocarbon polymer that contains the C-N key as material gas; Through RLSA (radial line slot antenna; Radial Line Slot Antenna) plasma CVD of mode (chemical vapour deposition, Chemical Vapor Deposition) injects formation luminescent layer 12 (a-CN:H on the transfer layer 11 in the hole xFilm).
Then, shown in Fig. 1 (c), on luminescent layer 12, form for example PBD (2-(4-trimethylphenylmethane base)-5-(4-xenyl)-1 through vapor deposition; 3,4-oxadiazole, 2-(4-tert-Butylphenyl)-5-(4-biphenylyl)-1; 3, the 4-oxadiazole) electron injecting layer 13 of Denging.
Then, shown in Fig. 1 (d), across pattern mask deposition targets atom (for example, Mg, Ag, Al etc.) on electron injecting layer 13, form the 2nd conductive electrode (negative electrode) 14 through sputtering method.Below, comprise that above-mentioned the 1st conductive electrode 10, hole inject transfer layer 11, luminescent layer 12, electron injecting layer 13 and the 2nd conductive electrode 14, be called organic element.
Then, shown in Fig. 1 (e), as mask, etched cavity is injected transfer layer 11, luminescent layer 12, electron injecting layer 13 with the 2nd conductive electrode 14.Afterwards, shown in Fig. 1 (f), the exposed portions serve of cleaning organic element and glass substrate G (the 1st conductive electrode 10) is removed the material that is adsorbed in organic element (for example organism etc.) (precleaning).
Then, shown in Fig. 1 (g), form SiN xThe sealing membrane 15 of film (silicon nitride film).Sealing membrane 15 forms through microwave plasma CVD.Particularly, the power through microwave excites the gas that contains silane or nitrogen to produce plasma body, uses the plasma body that produces, and forms fine SiN at the low temperature below 100 ℃ xFilm.Because the high temperature that organic EL reaches more than 100 ℃ then can suffer damage, so SiN xFilm need form with the low temperature process below 100 ℃.
In this embodiment, organic EL such as above forms illustratedly.In addition, a-CN:H xTherefore the luminescent layer 12 of film forms the hole in the bottom of luminescent layer 12 and injects transfer layer 11 because to be difficult to individual layer luminous, forms electron injecting layer 13 on top.
A-CN:H xFilm has the polymkeric substance shape structure that contains c h bond and C-N key.Here, reported a-CN:H xFilm observes strong PL (photoluminescence, Photo Luminescence) in room temperature.At this a-CN:H xIn the film forming of film, using methane and nitrogen, when plasma body (CCP) in the use parallel flat device or inductively coupled plasma (ICP), when the state that the electronic temp of plasma body is high carries out film forming, in film process, a-CN:H xC h bond in the film and C-N key are because the high frequency electric power that applies, and this key might be cut off, and cause the defective of dangling bonds in the film etc. multiple, therefore have the possibility of the deterioration of the characteristics of luminescence etc.
Therefore, in the film forming of the luminescent layer 12 of Fig. 1 of above-mentioned explanation (b), use the hydrocarbon gas, nitrogen or the ammonia that contain the C-N key, form luminescent layer 12 through the high density plasma RLSA mode of hanging down electronic temp.Because the plasma body that produces is low electronic temp, contained c h bond, the C-N key of material gas do not dissociate not superfluously.As a result, it is few and have an a-CN:H of stable c h bond, C-N key to form defectives as luminescent layer 12 xFilm.The characteristics of luminescence of the organic assembly (for example organic EL) of the luminescent layer 12 that use forms like this is good.In addition, generally speaking the electronic temp of the plasma body when using above-mentioned CCP is about 1～5eV at substrate surface, comparatively speaking, when using ICP, be 2～10eV, and the RLSA mode is 1～2eV, is lower than the electronic temp of other plasma source.In addition, the plasma density of above-mentioned CCP is 10 10Cm -3Below, the plasma density of ICP is 10 12Cm -3Below, with respect to this, be 10 in the RLSA mode 12Cm -3About, compare with other the density of plasma source more than equal.
As the above-mentioned hydrocarbon gas that contains the C-N key, can enumerate methylamine (CH 3NH 2), dimethylamine ((CH 3) 2NH), Trimethylamine 99 ((CH 3) 3N), pyridine (C 5H 5N) etc.The situation that contains c h bond or C-N key is also arranged in these material gas, if use the high plasma body of electronic temp carry out film forming then these keys the possibility of cut-out is arranged.Therefore, can know the high density plasma RLSA mode of when using these material gas, preferably hanging down electronic temp.
(base plate processing system)
Then, with reference to Fig. 2 the base plate processing system that is used to implement series of process shown in Figure 1 is described.The base plate processing system Sys that this embodiment is relevant comprises the combined substrate board treatment 1 with a plurality of treatment unit and the control device 20 of control basal plate treatment unit 1.
(substrate board treatment 1)
Substrate board treatment 1 comprises load lock LLM, carrying room TM (Transfer Module), cleaning chamber CM (Cleaning Module) and 6 technical module PM (Process Module) 1～6.
Load lock LLM is used for being carried to the vacuum carrying chamber that inside can be formed the decompression state of regulation of the carrying room TM that is in decompression state from the next glass substrate G of atmosphere system carrying.The carrying arm Arm of the multi-joint shape that the portion within it of being provided with among the carrying room TM can stretch and rotate.Begin most, use carrying arm Arm that glass substrate G is carried to cleaning chamber CM from load lock LLM, cleaning ITO surface.Afterwards, be carried to technical module PM1, be carried to other technical module PM2～PM6 again.In cleaning chamber CM, remove the pollutent (mainly being organism) that adheres on the surface of the ITO (anode layer) that is formed at glass substrate G through rayed etc.
In 6 technical module PM1～6, at first, form hole through vapor deposition on the ITO surface of glass substrate G at PM1 and inject transfer layer 11.Then, glass substrate G is carried to PM2, forms the luminescent layer 12 (a-CN:H that inject transfer layer 11 adjacency with the hole through RLSA mode plasma CVD xFilm).
Then, glass substrate G is carried to PM3, forms the electron injecting layer 13 of luminescent layer 12 adjacency through vapor deposition at PM3.Then, glass substrate G is carried to PM4, on electron injecting layer 13, forms the 2nd conductive electrode 14 at PM4 through sputter process.Then, glass substrate G is carried to PM5, carries out etch processes with the 2nd conductive electrode 14 as mask.Then, glass substrate G is carried to cleaning chamber CM, removes and in technology, is attached to the impurity such as organism that the exposed portions serve of transfer layer 11, luminescent layer 12, electron injecting layer 13 is injected in the hole.
Afterwards, glass substrate G is carried to PM6, forms for example by SiN through microwave plasma CVD xThe sealing membrane 16 that constitutes.
(control device 20)
Control device 20 is robot calculator of the integral body of control basal plate treatment system Sys.Particularly, the actual process of the carrying of the glass substrate G in the control device 20 control basal plate treatment system Sys and substrate board treatment 10 inside.Control device 20 has ROM22a, RAM22b, CPU24, bus 26, outer interface (exterior I/F) 28a and internal interface (inner I/F) 28b.
In ROM22a, the scheme of program that store the base program carried out at control device 20, starts when unusual and the process sequence of representing each PM etc.In RAM22b, store the data and the sequence of control that is used to carry out technology of the processing condition of each PM of expression.ROM22a and RAM22b are examples of storage media, can be EEPROM, CD, photomagneto disk etc.
CPU24 is controlled at glass substrate G and goes up the technology of making organic electronic devices through according to various scheme executive control programs.Bus 26 is paths of each device swapping data.In internal interface 28a input data, to there not being output data necessary such as illustrated watch-dog or loud speaker.Outer interface 28b is through transmitting and receiving data between network and the substrate board treatment 1.
For example, if send actuate signal from control device 20, then at substrate board treatment 1, the glass substrate G that carrying is indicated drives the PM that is indicated, and controls necessary technology, and informs control result's (acknowledge signal) at control device 20.Operation like this, control device 20 (robot calculator) is stored in the sequence of control of ROM22a or RAM22b through execution, and control basal plate treatment system Sys makes it accomplish the manufacturing process of organic EL (device) shown in Figure 1.
Then, the internal structure of each PM and the concrete processing of carrying out at each PM are described.In addition,, can use general device, omit the explanation of its internal structure carrying out each PM4 and PM5 that handles of etching and sputter.
(PM1: the vapor deposition treatment of transfer layer 11 is injected in the hole)
Fig. 3 is the schematic explanatory view of the vapor deposition treatment device 30 of PM1.The vapor deposition treatment device of representing among Fig. 3 30 forms the hole shown in Fig. 1 (a) through vapor deposition and injects transfer layer 11.In addition, it can be to overlap hole injection layer to become film formed layer with hole transporting layer that transfer layer 11 is injected in the hole, also hole injection layer and hole transporting layer can be set respectively.
Vapor deposition treatment device 30 has airtight processing vessel 31.In addition, in the front of processing vessel 31, be provided with and be used for the gate valve 32 that moving into of glass substrate G taken out of.
In the bottom surface of processing vessel 31, connection has the vapor pipe 33 of vacuum pump (not having diagram), and the inside of processing vessel 31 forms decompression state.In the inside of processing vessel 31, has the maintenance platform 35 that flatly keeps glass substrate G.Glass substrate G so that vapor deposition have the hole inject transfer layer 11 towards last supine state, carry to place and keep platform 35.Keep platform 35 on guide rail 36, to advance, carrying glass substrate G.
At the end face of 31 li of processing vessels, configuration vapor deposition head 37.Connect to supply with through pipe arrangements 39 at vapor deposition head 37 and form the steam supply source 38 of steam of film forming material that the CuPe (CuPc, Copper (II) Phthalocyanine) etc. of transfer layer 11 is injected in holes.Through the steam from 37 ejections of vapor deposition head from the film forming material of steam supply source 38 supplies, carrying simultaneously remains in the glass substrate G that keeps platform 35, and transfer layer 11 is injected in the formation hole on glass substrate G.
(PM2: luminescent layer 12 (a-CN:H xFilm) film forming is handled)
Then, glass substrate G is carried to microwave plasma processing apparatus PM2 according to the control of control device 20, shown in Fig. 1 (b), on transfer layer 11 is injected in the hole, forms a-CN:H xFilm.The longitudinal section of schematically representing the microwave plasma processing apparatus PM2 that the execution film forming is handled among Fig. 4.
Microwave plasma processing apparatus PM4 has the processing vessel 60 that open top has end cubic.Processing vessel 60 is for example formed and ground connection by aluminium alloy.Be provided with to carry in the bottom central of processing vessel 60 and put carrying of glass substrate G and put platform 61.Put platform 61 and connect high frequency electric sources 63 carrying, to apply the bias voltage of regulation through High frequency power in the inside of processing vessel 60 from high frequency electric source 63 outputs through coupling mechanisms 62.In addition, put platform 61 and connect high-voltage DC power supplies 65 carrying, through volts DS electrostatic adhesion glass substrate G from high-voltage DC power supply 65 outputs through coils 64.In addition, be embedded with well heater 66 carrying the inside put platform 61.Well heater 66 is connected with AC power 67, glass substrate G is remained on the temperature of regulation.
Dielectric plate 68 sealings that the opening at the top of processing vessel 60 is formed by quartz etc., and the resistance to air loss that keep in the treatment chambers through the O shape ring 69 that between processing vessel 60 and dielectric plate 68, is provided with.
Set radial line slot antenna 70 (RLSA:Radial Line Slot Antenna) on the top of dielectric plate 68.RLSA70 has the antenna body 70a of lower aperture, is formed with the aperture plate 70c in a large amount of slits across the dielectric plate 70b setting that is formed by low consumption dielectric material in the lower aperture of this antenna body 70a.
RLSA70 connects outside microwave generator 72 through coaxial wave guide 71.Be sent to the antenna body 70a of RLSA70 through coaxial wave guide 71 by microwave generator 72 microwaves output, for example 2.45GHz; After dielectric plate 70b short wavelengthization; Through each slit of aperture plate 70c, form circularly polarized wave and to processing vessel 60 internal feeds.
Upper portion side wall at processing vessel 60 is formed with the gas supply port 73 that is used for supply gas in a large number, and each gas supply port 73 is communicated with argon gas feed source 75 through gas pipeline 74.Be provided with the gas shower plate 76 of substantially planar in the substantial middle of treatment chamber.Gas shower plate 76 forms reticulation with the mode with the gas pipeline mutually orthogonal.Put platform 61 sides a large amount of pore 76a equally spaced are set carrying at each gas pipeline.The hydrocarbon gas C that contains the C-N key from the supply that is communicated with gas shower plate 76 xH yN zGas supply source 77a, supply with N 2Gas supply source 77b, the gas supply source 77c gas supplied of supplying with Ar discharge to glass substrate G equably from the pore 76a of gas shower plate 76.Here, as the hydrocarbon gas of supplying with from 77a, illustration methylamine (CH 3NH 2), dimethylamine ((CH 3) 2NH), Trimethylamine 99 ((CH 3) 3N), pyridine (C 5H 5N), from the 77b gas supplied except N 2Also can be NH in addition 4In addition, in processing vessel 60 inside, the upper space of gas shower plate 76 is called plasma excitation region A1, and the lower space of gas shower plate 76 is called diffusion plasma body zone A2.At plasma excitation region A1, generation has the plasma body than higher electronic temp, to the A2 diffusion of diffusion plasma body zone.
At processing vessel 60, through gas outlet pipe 78 gas barrier 79 is installed, through discharging the gas in the processing vessel 60, treatment chamber can be decompressed to required vacuum tightness.
In the microwave plasma processing apparatus PM2 that constitutes like this; Control based on control device 20; Through gas barrier 79 with the pressure-controlling in the treatment chamber for example below the 20mTorr, the power of supplying with the microwave in the treatment chambers from microwave generator 72 is controlled at 3.0W/cm 2More than; Carry and place with (for example handling near the temperature of indoor glass substrate G; Substrate surface temperature) be controlled at below 100 ℃, preferred below 70 ℃, supply with 50sccm argon gas (inactive gas) as plasma exciatiaon gas with this state from the gas supply port 73 of treatment chamber top.Supply with the hydrocarbon gas (C that 50sccm contains the C-N key from the gas shower plate 76 of treatment chamber central authorities xH yN zGas), 200sccm argon gas and nitrogen.Thus, the power through microwave produces and excites the plasma body with the argon of gas, by this plasma body mixed gas is activated.Low temperature at (below 70 ℃) below 100 ℃ forms luminescent layer 12 (a-CN:H xFilm).
(PM3: the vapor deposition treatment of electron injecting layer 13)
Then, glass substrate G is carried to evaporation coating device PM3 based on the control of control device 20, shown in Fig. 1 (c), on luminescent layer 12, forms electron injecting layer 13 through vapor deposition.Owing to use the identical device of vapor deposition treatment device 30 of representing PM1 with Fig. 3, so the explanation of omitting its internal structure as vapor deposition treatment device PM3.
(PM4: the sputter process of the 2nd conductive electrode 14)
Then; Glass substrate G is carried to PM4; Control based on control device 20; Excite gas supplied in processing vessel; Produce plasma body; Make the bombardment by ions target (sputter) in the plasma body of generation, the target atom that flies out from target is deposited on the electron injecting layer 13, forms the 2nd conductive electrode 14 (negative electrode) shown in Fig. 1 (d) thus.
(PM5: etch processes)
Then; Glass substrate G is carried to PM5; The plasma body that utilization excites etching gas to produce through the control based on control device 20 is a mask with the 2nd conductive electrode 14, and hole injection transfer layer 11, luminescent layer 12, electron injecting layer 13 are carried out dry etching.Thus, transfer layer 11, luminescent layer 12, electron injecting layer 13 are injected in the hole that forms shown in Fig. 1 (e).
(CM: precleaning)
Then, the control that glass substrate G gives control device 20 is carried to CM, uses the plasma body that excites argon gas and produce to remove and is attached to hole injection transfer layer 11, luminescent layer 12, the interface of electron injecting layer 13 or the impurity such as organism of exposed portions serve.
(PM6: the film forming of sealing membrane 15 is handled)
Then, glass substrate G is carried to microwave plasma processing apparatus PM6 based on the control of control device 20, shown in Fig. 1 (g), forms as SiN with the mode of exposed portions serve of sealing organic element xThe sealing membrane 15 of film (silicon nitride film).In addition, because the internal structure of microwave plasma processing apparatus PM6 is identical with the microwave plasma processing apparatus PM2 that Fig. 4 representes, therefore omit explanation here.
At microwave plasma processing apparatus PM6, give the control of control device 20, through vacuum unit 79 with the pressure-controlling in the treatment chamber for example below the 10mTorr, the power of the microwave of in treatment chamber, supplying with from microwave generator 72 is controlled at 4.0W/cm 2More than, carry to place and be controlled at below 100 ℃ with near temperature (for example substrate surface temperature) handling indoor glass substrate G, supply with 5～500sccm argon gas from top with this state, the silane (SiH that supplies with 0.1～100sccm from gas shower plate 76 4) gas, relatively, be to supply with at 1: 100 with the throughput ratio of silane gas and nitrogen.Thus, the power through microwave excites above-mentioned mixed gas, produces plasma body, uses the plasma body that produces to form SiN at low temperature xFilm (sealing membrane 15 of silicon nitride film).In addition, consider the influence to organic element, more preferably the surface temperature control of glass substrate G is below 70 ℃.
SiNx film (sealing membrane 15) in the protective membrane of organic element as the sealing membrane lamination.In order to maintain the moisture permeability resistance of the sealing film, the oxidation resistance inherent in the sealing film stress balance, SiNx film (sealing film 15) to thin to a certain extent, for example, the film thickness is preferably in the
Figure BPA00001434151900111
or less.
In the organic assembly of making according to the method for manufacture of the relevant organic assembly of this embodiment of above explanation, the CVD Cement Composite Treated by Plasma of the RLSA mode of, high density plasma low through the electronic temp of using the plasma body that produces forms luminescent layer 12 (a-CN:H xFilm).The processing space of the CVD plasma processing apparatus of RLSA mode as shown in Figure 4; Be divided into the plasma excitation region A1 and diffusion plasma body zone A2 that produce plasma body, the electronic temp of the plasma body among the diffusion plasma body zone A2 of treatment substrate is low to moderate about 1～2eV.Therefore, the possibility of the C-N key of the gas that uses in film forming cut-out is low.Like this, owing to can use the hydrocarbon gas that contains the C-N key, therefore can form the a-CN film efficiently as material gas.
Because the state low with the electronic temp of plasma body forms luminescent layer 12 (a-CN:H xSo contained C-N key can not cut off in the material gas, can keep luminescent layer 12 (a-CN:H film), xFilm) Nei C-N key.In addition, also can stably keep luminescent layer 12 (a-CN:H xFilm) c h bond of Nei other etc.At luminescent layer 12 (a-CN:H xFilm) in, owing to based on these C-N keys, c h bond and luminous, therefore stably contain the luminescent layer 12 (a-CN:H of these C-N keys, c h bond xFilm) very excellent as the stability of luminescent device, for example, the luminescent layer that uses in the organic assembly as organic EL etc. can use very effectively.
In addition, a-CN:H xFilm can be according to the amount control glow color of C-N key.In the present invention, through the feed rate of control, can control the amount of C-N key as hydrocarbon polymer, nitrogen or the ammonia of material gas use.
More than, an example of embodiment of the present invention has been described, but the present invention is not limited to illustrated mode.So long as those skilled in the art in the thought category that claims are put down in writing, can expect various modifications or revise example that these also belong to technical scope of the present invention certainly.
Fig. 5 is the sectional side elevation of the microwave plasma processing apparatus PM2 ' of the relevant RLSA mode of other embodiment of the present invention.In the structure of the microwave plasma processing apparatus PM2 ' that other embodiment is relevant,, the film forming of luminescent layer 12 supplies with N when handling 2The point of gas supply source 77b through 73 connections of gas pipeline 74 and gas supply port on different with above-mentioned embodiment.In addition, because the microwave plasma processing apparatus PM2 that other structure is correlated with above-mentioned embodiment is identical, therefore omit explanation.
The microwave plasma processing apparatus PM2 ' relevant according to other embodiment of representing among Fig. 5 is owing to supply with N at the plasma excitation region A1 of the inner upper of processing vessel 60 2Therefore gas can use the plasma exciatiaon N of the electronic temp with the diffusion plasma body zone A2 that is higher than processing vessel 60 inner belows 2Gas.The nitrogen-atoms that excites spreads to diffusion plasma body zone A2 from plasma excitation region A1.In diffusion plasma body zone A2, direct dissociated hydrocarbon gas and nitrogen-atoms are deposited on the glass substrate G with the state that contains the C-N key, carry out film forming.Therefore, can not add more nitrogen-atoms to bringing big infringement in the film forming luminescent layer 12.
In addition, in the above-described embodiment, the organic assembly that below element, obtains the bottom emissive type of light has been described, but the present invention is not limited thereto, also can use the organic assembly that above element, obtains the top emission structure of light.In addition, at this moment, the 2nd conductive electrode 14 is necessary for transparency electrode.
Utilizability in the industry
The present invention for example can be applicable to the amorphous hydrocarbon nitride (a-CN:H that the luminescent layer as organic EL device uses x) film film, use this amorphous hydrocarbon nitride (a-CN:H x) organic EL device and the method for manufacture thereof of film.

Claims (12)

1. amorphous hydrocarbon nitride (a-CN:H x) film of film, this film uses as the luminescent layer of organic assembly, and this film is characterised in that, comprising:
In processing vessel, supply with the operation of plasma exciatiaon as material gas with gas, the hydrocarbon gas that contains the C-N key and nitrogen or ammonia; With
Produce the plasma body of said plasma exciatiaon through microwave, make said material gas activatory operation through this plasma body with gas.
2. amorphous hydrocarbon nitride (a-CN:H as claimed in claim 1 x) film of film, it is characterized in that:
The hydrocarbon gas of the said C-N of containing key is methylamine (CH 3NH 2), dimethylamine ((CH 3) 2NH), Trimethylamine 99 ((CH 3) 3N), pyridine (C 5H 5N) any in.
3. amorphous hydrocarbon nitride (a-CN:H as claimed in claim 1 x) film of film, it is characterized in that:
In the generation of plasma body, use the RLSA mode.
4. the method for manufacture of an organic assembly is characterized in that:
On the handled object that is formed with the 1st conductive electrode, form the hole and inject transfer layer,
Inject the amorphous hydrocarbon nitride (a-CN:H of transfer layer superimposed layer as luminescent layer in said hole x) film,
At said amorphous hydrocarbon nitride (a-CN:H x) film superimposed layer electron injecting layer,
At said electron injecting layer superimposed layer the 2nd conductive electrode,
Lamination is to cover said handled object, the 1st conductive electrode, said hole injection transfer layer, said amorphous hydrocarbon nitride (a-CN:H x) sealing membrane that seals of the mode of film, said electron injecting layer, said the 2nd conductive electrode.
5. the method for manufacture of organic assembly as claimed in claim 4 is characterized in that:
Said amorphous hydrocarbon nitride (a-CN:H x) film, use the hydrocarbon gas contain the C-N key and nitrogen or ammonia as material gas, the power excitation material gas through microwave produces plasma body, and the plasma body that use is produced carries out film forming.
6. the method for manufacture of organic assembly as claimed in claim 5 is characterized in that:
The hydrocarbon gas of the said C-N of containing key is methylamine (CH 3NH 2), dimethylamine ((CH 3) 2NH), Trimethylamine 99 ((CH 3) 3N), pyridine (C 5H 5N) any in.
7. the method for manufacture of organic assembly as claimed in claim 5 is characterized in that:
In the generation of plasma body, use the RLSA mode.
8. the method for manufacture of organic assembly as claimed in claim 7 is characterized in that:
The plasma excitation region of activated plasma and the diffusion plasma body zone that substrate is handled are set in processing vessel; In said plasma excitation region, import nitrogen or ammonia, import the hydrocarbon gas that contains the C-N key to said diffusion plasma body zone.
9. organic assembly is characterized in that possessing:
Transfer layer is injected in the hole that on the handled object that is formed with the 1st conductive electrode, forms,
Inject the amorphous hydrocarbon nitride (a-CN:H as luminescent layer of transfer layer superimposed layer in said hole x) film,
At said amorphous hydrocarbon nitride (a-CN:H x) electron injecting layer of film superimposed layer,
The 2nd conductive electrode of said electron injecting layer superimposed layer and
To cover said handled object, said the 1st conductive electrode, said hole injection transfer layer, said amorphous hydrocarbon nitride (a-CN:H x) sealing membrane that seals of the mode of film, said electron injecting layer, said the 2nd conductive electrode.
10. organic assembly as claimed in claim 9 is characterized in that:
Said amorphous hydrocarbon nitride (a-CN:H x) film, use the hydrocarbon gas contain the C-N key as material gas, the power activated plasma through microwave excites the plasma exciatiaon material gas that produces with gas, carries out film forming.
11. organic assembly as claimed in claim 10 is characterized in that:
The hydrocarbon gas of the said C-N of containing key is methylamine (CH 3NH 2), dimethylamine ((CH 3) 2NH), Trimethylamine 99 ((CH 3) 3N), pyridine (C 5H 5N) any in.
12. organic assembly as claimed in claim 10 is characterized in that:
In the generation of plasma body, use the RLSA mode.
CN2010800118272A 2009-03-13 2010-03-11 Method of depositing amorphous hydrocarbon nitride (a-CN:Hx) film, organic EL device, and process for producing same Pending CN102348777A (en)

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