CN106092928A - A kind of method utilizing plasma etching in site measurement polymeric sublayer spectrum - Google Patents
A kind of method utilizing plasma etching in site measurement polymeric sublayer spectrum Download PDFInfo
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Abstract
The invention discloses a kind of method utilizing plasma etching in site measurement polymeric sublayer spectrum, comprise the following steps: 1) in transparent glass substrate, prepare thin polymer film；2) absorption spectrum of ultraviolet-uisible spectrophotometer test polymer thin film is utilized；3) utilizing oxygen plasma etch progressively etch polymers thin film, oxygen plasma air pressure is 1 20 Pascals；Etching occurs at polymeric film surface and progressively reduces film thickness, and in situ detection absorption spectrum；4) absorption spectrum of each subgrade of thin polymer film is obtained according to the decrement of absorbance at each wavelength.The present invention, by conventional laboratory installation, utilizes the surface selective etching technology of simple optical means and plasmaassisted directly to test subgrade absorption spectrum.Utilize the change of spectrogrph real-time detection absorption spectrum, parse the absorption spectrogram at different depth.The present invention can be used for the multiple physical quantity in Study Polymer Melts thin film at different depth position.
Description
Technical field:
The invention belongs to material spectrum analysis technical field, be specifically related to one and utilize plasma etching in site measurement to gather
The method of compound subgrade spectrum.
Background technology:
Polymer is because having the feature such as flexibility, cheap, easy processing, and all obtaining in the various aspects produced and live should
With.In addition to polymer body phase material, the application of thin polymer film and ultrathin membrane is the most extensive.As a example by conjugated polymer, altogether
Conjugated polymer thin film is in fields such as Organic Light Emitting Diode, field-effect transistor, macromolecule thermo-electric device, solaodes
Obtain and study 1,2 widely.The energy gap of organic/polymer semiconductor is the most narrow (1-3 electron volts), so having the strongest
Visible light absorption 3-7.The optical absorption peak position of polymer is relevant with several factors with intensity: 1) polymer molecule is long,
Can regard as and be made up of different segments, the different HOMO between segment is different with lumo energy, thus cause thin film energy
The dispersibility of gap；2) polymer molecular weight has polydispersity；3) crystalline polymer is usually hemicrystalline, in thin film simultaneously
There is amorphous phase and crystallization phase, its respective molecular conformation difference is relatively big, and corresponding optical absorption characteristic also has notable difference；4)
Thin film Middle molecule is oriented in film surface and inside is different.Above-mentioned four kinds of reasons show, in polymer thin-film material, thin
The optical absorption characteristic of film is different in the internal different degree of depth of thin film.On the other hand, a lot of conjugated polymers electricity
Sub-device uses blend thin films, then in blend, device performance is had the biggest by the distribution in depth of film direction of each component
Impact.Such as, in polymer p-n bulk-heterojunction solaode, p-type material needs and anode connects, and n-type material needs
To connect with negative electrode, and p-type material and n-type material need to form interpenetrating networks in the film and could effectively transmit electric charge, thus
Realize high photoelectric transformation efficiency.But, scientific research personnel there is presently no direct way and measures thin polymer film depth resolution
Absorption spectrum.
We continue as a example by polymeric acceptor phase hetero-junction thin-film solar photovoltaic material below, talk subgrade absorption spectrum
Importance.Bulk-heterojunction photovoltaic device obtains the green grass or young crops of people due to character such as its flexibility, low cost, solution machinabilitys
Looking at, the efficiency of report alreadys more than 10% recently, it is shown that bright Research Prospects 8,9.Different with the organic film of stratiform
It is, the composite that bulk-heterojunction is made up of biphase or polyphase blend that component includes p-type electron donor and N-shaped electricity
Sub-receptor.Donor and receptor be mutually mixed form and the component ratio along thin film longitudinal direction directly affects the light of device
Photoelectric transformation efficiency, because these parameters and exciton produce, energy/electric charge shifts and electric charge transmission is closely related.Therefore, in order to
Optimize the electricity conversion of photovoltaic film, it would be desirable to analyze sunlight and decay the most in the film, and photon
The position that attenuating position and exciton produce；And need to set up the optical property of depth resolution and device performance.Although along light
The light intensity attenuation process of volt thin film longitudinal direction can be come by the way of computer simulation according to device architecture and blending ratio
Prediction, and the direct experiment of these optical properties is observed and is not the most reported.In recent years, some complex technology, the most logical
Crossing ultramicroscope and thin-membrane section carries out imaging, three-dimensionalreconstruction transmission electron microscope 10, for characterizing depth resolution
Component is distributed.On the other hand, use continuous lithographic technique and dynamic secondary mass spectrum or x-ray photoelectron spectroscopy also by success
Application and photovoltaic polymeric films.But, these methods or the experimental provision of needs complexity and the longest operating time, or
Signal to noise ratio is relatively low, or the shortcoming such as acquired results information contained amount is little.Such as three-dimensionalreconstruction transmission electron microscope, material
Need that there is higher contrast and higher electron radiation stability；For neutron reflection, need in expensive large scientific facilities
Component；For dynamic secondary mass spectrum, people need isotope labelling.But, these non-optical means can not provide light thin
Propagation law in film and dampening information, can not provide the position etc. that exciton produces.
UV-vis absorption spectrum is a kind of very conventional analytical technology, be widely used in chemical, medicine,
The field such as environment, inspection and quarantine.In polymer solar battery field, ultraviolet-visible absorption spectroscopy is usually used to characterize solar energy
Sunlight is responded by battery, although it is lower-cost measuring technology, can provide about film microstructure and composition
Circumstantial evidence.
In this context, we plan to be devoted to etch with continuumpiston in this project, and in-situ test material
The optical absorption spectra of material.Use continuous Beer-Lambert law and suitable simplified model, it is achieved the depth resolution of thin film
Optical absorption spectra, thus provide for membrane structure analysis, light-matter interaction, photoelectric device performance optimization etc. and support.
List of references:
1. river is bright；Mansion longevity width, the proposition in modern age of polymer science. first edition ed.；Publishing house of Fudan University: Shanghai,
1998.
2. primary track is originally, functional material chemical progress. first edition ed.；Chemical Industry Press: Beijing, 2005.
3.Sirringhaus,H.；Brown,P.J.；Friend,R.H.；Nielsen,M.M.；Bechgaard,K.；
Langeveld-Voss,B.M.W.；Spiering,A.J.H.；Janssen,R.A.J.；Meijer,E.W.；Herwig,P.；de
Leeuw,D.M.,Two-dimensional charge transport in self-organized,high-mobility
conjugated polymers.Nature 1999,401,(14),685-688.
4.Friend,R.H.；Gymer,R.W.；Holmes,A.B.；Burroughes,J.H.；Marks,R.N.；
Taliani,C.；Bradley,D.D.C.；Dos Santos,D.A.；Brédas,J.L.；M.；Salaneck,
W.R.,Electroluminescence in conjugated polymers.Nature 1999,397,(6715),121-
128.
5.Sun,Y.；Sheng,P.；Di,C.；Jiao,F.；Xu,W.；Qiu,D.；Zhu,D.,Organic
Thermoelectric Materials and Devices Based on p-and n-Type Poly(metal 1,1,2,
2-ethenetetrathiolate)s.Adv.Mater.2012,24,932-937.
6.He,Y.；Wu,W.；Zhao,G.；Liu,Y.；Li,Y.,Poly(3,6-dihexyl-thieno[3,2-b]
thiophene vinylene):Synthesis,Field-Effect Transistors,and Photovoltaic
Properties.Macromolecules 2008,41,(24),9760-9766
7.Guo,Y.；Di,C.-a.；Ye,S.；Sun,X.；Zheng,J.；Wen,Y.；Wu,W.；Yu,G.；Liu,Y.,
Multibit Storage of Organic Thin-Film Field-Effect
Transistors.Adv.Mater.2009,21,1954-1959.
8.You,J.；Dou,L.；Yoshimura,K.；Kato,T.；Ohya,K.；Moriarty,T.；Emery,K.；
Chen,C.-C.；Gao,J.；Li,G.；Yang, Y., A polymer tandem solar cell with 10.6%power
conversion efficiency.Nat.Commun.2013,4:1446doi:10.1038/ncomms2411.
9.Liang,Y.；Feng,D.；Wu,Y.；Tsai,S.-T.；Li,G.；Ray,C.；Yu,L.,Development of
New Semiconducting Polymers for High Performance Solar Cells
J.Am.Chem.Soc.2009,131,(22),7792-7799.
10.Oosterhout,S.D.；M.Wienk,M.；Bavel,S.S.v.；Thiedmann,R.；Koster,
L.J.A.；Gilot,J.；Loos,J.；Schmidt,V.；Janssen,R.A.J.,The effect of three-
dimensional morphology on the efficiency of hybrid polymer solar
cells.Nat.Mater.2009,8,818-824.
Summary of the invention:
It is an object of the invention to provide a kind of method utilizing plasma etching in site measurement polymeric sublayer spectrum.
For reaching above-mentioned purpose, the present invention adopts the following technical scheme that and realizes:
A kind of method utilizing plasma etching in site measurement polymeric sublayer spectrum, comprises the following steps:
1) preparing thin polymer film in transparent glass substrate, polymer film thickness is 20-200 nanometer；
2) utilizing the absorption spectrum of ultraviolet-visible spectrophotometer test polymer thin film, wherein, test pattern is transmission
Pattern；
3) utilizing oxygen plasma etch progressively etch polymers thin film, etching speed 1 nm/sec, oxygen plasma is put
Electric power range 20-200 watt, oxygen plasma air pressure is 1-20 Pascal；Etching occurs at polymeric film surface and progressively
Reduce film thickness, and in situ detection absorption spectrum, determine the polymer thin thickness in etching process by atomic force microscope
The change of degree；
4) absorption spectrum of each subgrade of thin polymer film is obtained according to the decrement of absorbance at each wavelength, wherein,
The depth location at each subgrade place is determined by atomic force microscope.
The present invention is further improved by, and polymer thin-film material is soluble polythiophene.
Relative to prior art, the present invention has a following beneficial effect:
The innovation of the present invention is, it is achieved absorption spectrum (the subgrade absorbing light at thin-film material different depth position
Spectrum).
In order to optimize the electricity conversion of photovoltaic film, the present invention analyzes sunlight and decays the most in the film,
And the position that the position that is absorbed by material of photon and exciton produce；And need to set up the optical property of depth resolution and device
Performance.Although the light along thin film longitudinal direction absorbs information can pass through computer simulation according to device architecture and blending ratio
Mode predict, and the direct experiment of these optical properties observe the most do not report.In recent years, some complex skills
Art, such as, carry out imaging by ultramicroscope to thin-membrane section, three-dimensionalreconstruction transmission electron microscope, neutron reflection and ellipse
Circle light polarization technology is constantly studied, for the component distribution characterizing depth resolution.On the other hand, etching continuously is used
Technology and dynamic secondary mass spectrum or x-ray photoelectron spectroscopy are also successfully applied and photovoltaic polymeric films.But, these
Method or need complicated experimental provision and the longest operating time, or signal to noise ratio is relatively low, or acquired results is contained believes
The shortcomings such as breath amount is little.Such as three-dimensionalreconstruction transmission electron microscope, material needs have higher contrast and higher electricity
Sub-irradiation stability；For neutron reflection, need expensive large scientific facilities neutron source；For dynamic secondary mass spectrum, Ren Menxu
Want isotope labelling.Nonetheless, these non-optical means can not provide light propagation law in the film and dampening information,
The position etc. that exciton produces can not be provided.Under this research background, the present invention realizes polymer thin by oxygen plasma
Film surface selective etching, it is thus achieved that the absorption spectrum (subgrade absorption spectrum) at material different depth position, has significantly innovation
Property.
The present invention contributes to people and explores membrane structure and the relation of performance, provides spectrum for exploitation solar energy photovoltaic material
Data.It addition, subgrade absorption spectroscopy techniques is expected to be developed further into merit In situ spectroscopic analyser, obtain in film analysis field
Extensively application.
Accompanying drawing illustrates:
Fig. 1 is the subgrade absorption spectrum of P3BT/a-PS (50wt%P3BT) blend film (thickness 80-100nm), utilizes former
Position oxygen plasma etch obtains.Spectroscopic data has moved with convenient reading in vertical coordinate direction, the subgrade that spectrum is corresponding
Thickness of substantially equal (about 15nm).
Fig. 2 is the three-dimensional electronic microgram of P3BT/a-PS (50wt%P3BT) blend film (thickness 80-100nm).Figure
2a-f figure is all the two-dimentional sectional drawing at different depth along horizontal xy face: wherein Fig. 2 a is bottom thin film；Fig. 2 b-d is in thin
In the middle of film；Fig. 2 f is near thin film upper surface.Electron microscope picture in this figure is at paper (Advanced Materials
2014,26,2359) deliver in, here with this microscope figure original position subgrade abosrption spectrogram in edition with parallel text is invented.
Fig. 3 is that thickness is about poly-(3-butyl thiophene)/polystyrene (P3HT/PS) of 20nm (P3BT mass fraction is
5%) the subgrade abosrption spectrogram of laminated film.
Fig. 4 is the Surface absorption spectrogram of tri-kinds of laminated films of P1:PCBM, P2:PCBM, P2:PCBM, wherein P1, P2, P3
Paper (Advanced Materials 2015,10.1002/adma.201502900) is seen with PCBM definition.
Detailed description of the invention:
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Embodiment 1:
The method utilizing solution spin coating prepares poly-(3-butyl thiophene)/polystyrene (P3BT/ that thickness is about 90nm
PS) (P3BT mass fraction is 50%) laminated film.Thin film is etched under oxygen plasma, and in situ detection absorption spectrum
(etching condition: power 30 watts；Air pressure 10 Pascal).Test result is as shown in Figure 1.In the present embodiment, in absorption spectrum
The absworption peak of 500nm adnexa corresponds to P3BT, and the absworption peak near 200nm is corresponding to PS.Can be seen by subgrade absorption spectrum
Going out, P3BT has in different subgrades and is distributed.This is corresponding with the three-dimensional electronic microscope figure of Fig. 2.
Embodiment 2:
The method utilizing solution spin coating prepares poly-(3-butyl thiophene)/polystyrene (P3HT/ that thickness is about 20nm
PS) (P3BT mass fraction is 5%) laminated film.Thin film is etched under oxygen plasma, and in situ detection absorption spectrum (is carved
Erosion condition: power 30 watts；Air pressure 10 Pascal).Test result is as shown in Figure 3.In the present embodiment, in absorption spectrum
The absworption peak of 500nm adnexa corresponds to P3HT, and the absworption peak near 200nm is corresponding to PS.Can be seen by subgrade absorption spectrum
Going out, P3HT is mainly distributed on the upper surface of thin film.
Embodiment 3:
P1 is prepared according to paper (Advanced Materials 2015,10.1002/adma.201502900):
Tri-kinds of laminated films of PCBM, P2:PCBM, P2:PCBM (paper is shown in P1, P2, P3 and PCBM definition).By thin film at oxygen plasma
Lower etching, and in situ detection absorption spectrum (etching condition: power 30 watts；Air pressure 10 Pascal).On the laminated film obtained
Absorption spectrum result is as shown in Figure 4 on surface (corresponding to the subgrade thin film of 0-5nm).In the present embodiment, at 600nm in absorption spectrum
The absworption peak of adnexa corresponds to polymer (P1, P2 or P3), and the absworption peak near 300nm is corresponding to PCBM.Inhaled by subgrade
Receive spectrum it can be seen that PCBM has more distribution in the upper surface of P3:PCBM laminated film, and at P1:PCBM and P2:PCBM
Laminated film upper surface is distributed less, well explains the difference about Photovoltaic Properties in paper.
For understanding further to the present invention, now its know-why is made as described below:
According to Beer-Lambert law, the absorbance of thin film is defined as A=-logI/I0Or I=I010-A, wherein I
And I0It is respectively transmission and incident intensity.We can assume that thin film is made up of n-layer film sub-layer, and each subgrade has suction
Luminosity Ai(i=1,2,3 ..., n).Therefore, the light intensity after incident illumination have passed through n subgrade is:
This explanation total absorbance of thin film is equal to the linear superposition of each subgrade absorbance.Therefore, if we can look for
To suitable plasma etching technology, allow etching occur at film surface and progressively reduce film thickness, then in principle I
Be possible by situ detection absorbance during etching, and obtain surface according to the decrement of absorbance and each is sub-
The absorbance of layer.
From the point of view of conjugated polymer thin films material, the orientation of polymer molecular chain counter substrate often decides material
Photoelectric properties.When the thickness of thin film and polymer chain length are suitable, molecule is not in the conformation within film surface and thin film
With.In continuous etching process, in-situ applications ultraviolet-visible absorption spectroscopy, obtain table according to continuous Beer-Lambert equation
Face and subgrade absorption spectrum.So, peak position and intensity according to spectrum we can determine whether that molecularly oriented and conformation are at thin film table
Face and internal difference.
Oxygen plasma etch is that a kind of substrate widely used at research laboratory cleans and lithographic technique.Oxygen etc.
Gas ions contains multiple reactive component, including O2 +,O2 -,O3,O,O+,O-, ionizing ozone and metastable state oxygen excited state
Deng, and these components with the strongest reactivity can be from the continuous etachable material in organic film surface.Oxygen plasma exists
During etch polymers thin film, etching mainly etches downwards from upper surface..
If in etching process, the roughness of thin film and crystal size or separated size are much smaller than incident light wave
Long, then the light scattering effect during incident light propagation is the most weak, thus scattered light intensity approximation can be ignored.Fortunately,
At present great majority have film thickness corresponding to the organic polymer photoelectric device of superior performance all at 100 ran, its knot
Brilliant size or separated size also mostly 10-20 nanometer (yardstick that is separated excessive typically there is poor device
Can).So in light communication process, we typically can be without the concern for scattered light.It addition, in the test of organic film, instead
Penetrate light to approximate and be not considered.Therefore, the change acquisition degree of depth of in-situ test absorbance during surface etch is divided
The optical absorption spectra distinguished, is practicable in principle and operation.
How to realize the surface selective etching of thin polymer film？We were previously noted, and oxygen plasma contains multiple
Reactive component, including O2 +,O2 -,O3,O,O+,O-, ionizing ozone and metastable state oxygen excited state etc., and these have very
The component of strong reactivity can be from the continuous etachable material in organic film surface.Therefore, if oxygen plasma pressure is higher
If, these active components can be diffused into below film surface, it is possible to and component generation oxidoreduction within thin film
Reaction, changes the optical absorption characteristic of thin film internal material, brings a lot of difficulty to parsing subgrade film absorption spectrum.Therefore,
Etching process should allow as far as possible oxygen plasma pressure be maintained at relatively low level (within 20 handkerchiefs).
In thin film etching process, thickness change can be obtained by means such as x-ray reflections.
In general, oxygen plasma is interacted different by different organic or polymeric materials, thus etch rate
Difference.Although we analyze, if surface roughness is less in composite material film (roughness is less than thickness 5%)
And separated yardstick the least time, can approximate and ignore the error that each component etch rate difference causes.This is because, in position
During dry etching, the fast phase of etch rate will necessarily protecting by the slow phase of etch rate.Whole etching process
Each component etch rate approximately equal can be regarded as.Although we can be come composite by the etch rate of pure component
Experimental result is corrected, but each component etch rate in the composite and the etch rate in pure component are also not
With, bring the biggest difficulty to the resultant error corrected out assessment.But, the most appropriate a kind of control experiment is, from thin
Two different surfaces of film carry out separate etch experiment, the simultaneously change of in situ detection absorption spectrum to sample.We can be by
Thus obtained two groups of subgrade absorption spectrums are averaged, and acquired results will be closer to real result.
Finally, let us analyzes the spatial resolution of lower subgrade absorption spectrum.Ultraviolet-visible absorption spectroscopy is one and answers
By extensive and that sensitivity is the highest technology, have in the sensitivity in the past few decades of spectrogrph itself and be greatly improved, be
The high-resolution guarantee of this project.Common conjugated polymer thin film, as a example by 100 nano thickness, if etching reaches 1% thickness
Degree, namely 1 nanometer, what spectrogrph can be the sensitiveest detects.This also just says, the sky of this project institute Dalmatia layer absorption spectrum
Between the restraining factors of resolution not at spectrogrph.Because the roughness of general thin film is typically more than 1 nanometer, therefore our method
Depth resolution mainly affected by the roughness of thin film.For general homopolymer, etching process keep thin film coarse
Degree is feasible in 5 nanometers.And 5 nanometers are the least relative to whole film thickness (100 ran).But, altogether
The etch rate of each component of mixed thing usually has larger difference, and this is that the popularization of this technology brings difficulty.Fortunately,
There is the separated yardstick of organic photoelectric polymer blend film of superior performance typically below 10 nanometers, such as, for having
From the point of view of body phase heterojunction solar battery, exciton dissociation length is typically below 10 nanometers, and excessive two-phase laminated flow is necessarily led
Cause the reduction of performance.Because biphase separated yardstick is much smaller than film thickness, so, in position during dry etching, etching
The fast phase of speed will necessarily protecting by the slow phase of etch rate.Whole etching process can regard each component etching speed as
Rate approximately equal.So, for heterogeneous system, if the yardstick that is separated is the least, we still are possible to thin film
Roughness control below 5 nanometers, say, that our method can realize being better than the depth resolution of 5 nanometers.Luckily
, for analyzing the character research aspect of light absorption film, the resolution of 5 nanometers is the most enough at a lot of aspects.
The shortcoming that the present invention exists:
The thickness of semiconductor film that organic electro-optic device is corresponding is typically small, in 100 ran or following resolution.
So resolution of subgrade absorption spectrum needs in principle far below film thickness, could effectively apply and test at material characterization
Field.So, this method is only applicable to the thin film that surface roughness is low, thickness is homogeneous, the yardstick that is separated is little.
For general homopolymer, keeping Film roughness in etching process is feasible in 5 nanometers.And 5 nanometers
It is the least relative to whole film thickness (100 ran).But, the etch rate of each component of blend usually has
Larger difference, this is that the popularization of this technology brings difficulty.
Oxygen plasma body method progressively can etch with noresidue comprise only the element such as C, H and O or S polymer or
Organic molecule, reason is oxygen plasma and these Element generation volatizable material in etching process.But, if in material
When being difficult to, containing other, the element generating volatilizable thing with oxygen plasma, such as metallic element or Si etc., in etching process
The deposit of middle generation can hinder carrying out further of etching.If sedimentary particle is excessive, can seriously increase the coarse of thin film
Degree, reduces the depth resolution of this method application.
Claims (2)
1. the method utilizing plasma etching in site measurement polymeric sublayer spectrum, it is characterised in that include following step
Rapid:
1) preparing thin polymer film in transparent glass substrate, polymer film thickness is 20-200 nanometer；
2) utilizing the absorption spectrum of ultraviolet-visible spectrophotometer test polymer thin film, wherein, test pattern is Transmission Modes
Formula；
3) oxygen plasma etch progressively etch polymers thin film, etching speed 1 nm/sec, oxygen plasma electric discharge merit are utilized
Rate scope 20-200 watt, oxygen plasma air pressure is 1-20 Pascal；Etching occurs at polymeric film surface and progressively to reduce
Film thickness, and in situ detection absorption spectrum, determine polymer film thickness in etching process by atomic force microscope
Change；
4) absorption spectrum of each subgrade of thin polymer film is obtained according to the decrement of absorbance at each wavelength, wherein, each
The depth location at subgrade place is determined by atomic force microscope.
A kind of method utilizing plasma etching in site measurement polymeric sublayer spectrum the most according to claim 1, its
Being characterised by, polymer thin-film material is soluble polythiophene.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111537539A (en) * | 2020-05-12 | 2020-08-14 | 西安交通大学 | Method for measuring photoelectron spectrum of polymer sublayer by plasma etching |
| CN111707635A (en) * | 2020-05-15 | 2020-09-25 | 西安交通大学 | Method for measuring component distribution in depth direction of organic film by plasma etching |
| CN113376098A (en) * | 2021-06-17 | 2021-09-10 | 陕西师范大学 | Monitoring device for in-situ monitoring of film formation and crystallization of semiconductor material and use method |
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| CN106092928B (en) | 2018-12-07 |
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