~v~- j2,03491 2 0 ~ 9 4 8 ~ Pcr/GBgl/0l42l PATTERNING OF-SEMICONDUCTIVE POLYME~S
: , FIELD OF THE INVENTION
This invention relates to patterning of semiconductive .
polymers to provide continuous polymer films having different regions of different characteristics.
BACKGROUND TO THE INVENTION
It has been shown tha~ certain conjugated polymers show a relatively high quantum efficiency for the radiative deray of singlet excitons. Of these, poly-p-phenylene vinylene (PPV) can be prepared via a solution-processible precursor polymer, and although itself intractable and not easily processed, can be prepared in the form of thin films of hi~h quality by thermal conversion of the as-prepared films of the precursor polymer. Details of this.general synthesis method are given in "Precursor route poly(p-phenylene vinylene): polymer characterisation and control of electronic properties", D.D.C.
Bradley, J. Phys. D: Applied Phys. 20, 1.389 (1987), and "Spectroscopic.and cyclic voltammetric ~tudies of ~^ polytp-phenylene vinylene) prepared from two different sulphoni ~ salt precursor polymers", J.D. Stenyer-Smith, R~W.
Lenz and 5. Wegner, Polymer 30, 1048 (1989). Measurements of photoluminescence, PL, ha~e been reported by for example "Optical Investigations o~ Conjugated Polymers", R.H~ Friend, J. Molecular Electronics, 4, 37 (1988), and "Photoexcitation in Conjugated Pol~mers", R.H. Friend, D.D.C. Bradley and P.D.
Townsend, J. Phys. D 20, 1367 (1987). In our ea_lier International Patent Application No. PCT/GB90/00584 films of PPV arP disclosed as being useful as the emissive layer in a structure exhibiting electroluminescence (EL). This structure .~ .
~092/OW91 - 2 _ 2 0 8 9 ~ ~ ~ PCT/GB91/01421 requires injection of electronS and holes from either side of the active (l.e. emlssive) region of the film, and various metallic contact layers can be used. In sandwich-likP
structures, and for emission from the plane of the device, one of these should be semi-transparent.
The advantages of using polymers of this type as the emissive layer in EL structures include:
(a) ease of ~abrication of large area structures.
Various methods are available for solution-processing of the precursor polymer, including spin-coating from solution which is the preferred method, and dip-coating;
(b) intractability of the polymer film, giving desirable strength, resistance to degradation from heat and exposure to oxygen, resistance to structural changes such as recrystallisation and shrinkage, and resistance to ion migration;
(c) intrinsically good properties for luminescence, including low densities of charges and/or spin-carrying defects.
However, a severe restriction has been placed on the use of such polymers by virtue of the fact that each continuous polymer film has the same characteristics throughout. That is, the quantum ef~iciency, wavelength of radiation and -~
refractive index are the same over the whole surface of the film.
It is an object of the invention to provide a method of forming a polymer layer having different regions of different characteristics.
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~ 92/0~91 PCT/~B91/01421 ~ 3 ~ 20~9`~81 SUMMARY OF THE INVENTION
The present invention provides of forming in a semiconductive conjugated polymer at least first and sPcond regions having different optical properties, the method comprising: forming a layer of a precursor polymer and permitting the first region to come into contact with a reactant and heat while permitting the second region to come into contact with a lower concentration of the reactant, the reactant affecting the conv`ersion conditions of the precursor polymer in such a way as to control the optical properties of at least the first region so that the optical properties of the first region are different from those of the second region. The first and second regions are ~ypically adjacent one another.
Advantageously, the precursor polymer comprises a poly(arylene~ -ethanediyl) polymer, at least some of the ethane groups of which include a modifier group whose susceptibility to elimination is increased in the presence of the reactant. Preferably, the reactant is an acid. The acid may be used which assists elimination of the modifier group.
The acid may be added to the precursor polymer or may be endogenous ~o the precursor polymer, for example t~e acid evolved during formation of the precursor polymer. All that is required is that the first region comes into contact with the acid whereas the second region does not.
The modifier group should be stable at ambient temperatures and should preferably ~e stable to heat in the absence of ~he reactan~. Typical modifier groups are discussed in more detail below.
Preferably the heating is carried out in the temperature range l00 to 300C. The heating is preferably carried out for l to 24 hrs.
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Preferably, t~e conjugated polymer is a copolymer comprising at least two different monomer units which in their individual nomopolymer forms have different bandgaps. The proportian of monomer units in the copolymer m~y be selected to control the optical properties of the copolymer. By controlling the optical properties of the copolymer, the wavelength of radiation emitted during luminescence can be selected. The quantum efficiency of the copolymer may also be enhanced by controlling the optical properties. The refractive index of the copolymer may also he selected by controlling the optical properties thereof. Our copending application No.
(Page White ~ Farrer Ref: 69117) describes and claims methods of modulating the semiconductor bandgap so as to control the optical properties of the copolymar.
A semiconductor is a material that is able to acco~modate charged excitations which are able to move through this material in response to an applied electrical field. Charge excitations are stored in the semiconductor in states which are (or are derived from) conduction band states (in the language of quantum chemisty, lowest unoccupied molecular orbitals, LUMOs) if negatively charged, or valence band states (high~st occupied molecular orbitals, HOMOs) if positively charged. The semiconductor band gap is the energy difference between valence and conduction bands (or from HOMO to LUMO) The present application is primarily concerned with copolymers in which the material is made up of chemically distinct regions of polymer chain. A convenient description of the electronic states (molecular orbitals) is one in which the wavefunctions are substantially localised on a region of change of one chemical type. It is useful to define the semiconduc~or bandgap locally, i.e. as the energy gap between HOMO and LUMO on a particular sequence of polymer chain to which the HOMO and LUMO wavefunc~ions are substantially confined. One can expect to find a variation of gap from HOMO
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~)2/0~91 2 0 8 9 ~ PCT/GB91/01421 to L~O between reyions of one chemical type and those of another. This may be described as a spatial modulation of the bandgap.
The conjugated polymers used here are all examples of semiconductors, and there is some control of bandgap throuyh adjustment of the repeat units of the chain. However, it is also found that it is useful to incorporate some units of non-conjugated polymers to form some of the copolymers. In this`case, the non-conjugated section of the chain would function as a very large gap semiconductor, so that under the conditions of opexation found here it would behave as an insulator, i.e. there would be little or no charge storage on or movement through such a region of the chain. In this case, the material as a whole will still function as a semiconductor so long as there is a path through the bulk of the sample that passes entirely through the semiconducting regions of the chain (those that are conjugated). The threshold for the existence of such a path is termed the percolation threshold, and is usually found to be in the region of 20~ volume fraction of non insulating material. In the present specification, all such co-polymers are well above this percolation threshold and can be termed as semiconductors.
Quantum efficiency for luminescence may be de~ined as photons per electronic excited state. For photoluminescence this is identified as photons out per photon absorbed. For electroluminescence this is defined as photons out p~r electron injec~ed into the structure.
A number of matho~s are available for causing the first region of the polymer to come into contact with the reactant and heat ; 30 while premi~ting the second region to come into contact with a lower concentration of the reactant. In one embodiment, the step of permitting the first region to come into contact with the reactant comprises applying a coating in a desired pattern w092~0~91 2 0 8 9 ~ 81 PCT/GB91/01421~`, to the surface of the layer of the pre~ursor polymer so as to leave unprotected portions of the surface. A reactant is applied to those unprotected portions. Alternatively, the reactant may be endogenous acid present in the layer of the precursor polymer. In this embodiment, the step of permitting the first region to come into contact with the reactant comprises trapping the acid during heating by a coating applied in a desired pattern to the surface of the layer of the precursor polymer. In either embodi~ent, ~he coating may be applied in the desired pattern by coating the sur~ace of the layer of the precursor polymer with a layer of the coating. A layer of photoresist is applied to the layer of the coating and the layer o~ photoresist is activated so as to render the coating in the desired pattern protected by the photoresist. Any suitable photoresist may be used, such as one with optical or electron-beam sensitivity. The unprotected coating is removed, for example by etching and the remaining photoresist is also removed so as to leave the coating. In this way, the coating may ~e patterned with high resolution.
The particular material used to form the coating is not critical provided that it can be patterned on top of ~he layer of the precursor polymer without damaging the pol~mer underneath. The coating must be able to withstand the temperatures used in the heating and must also be subsequently removable without damaging the converted polymer. The preferred coating is aluminium although other metals may be usable as may some silicone-containing organic resists. An effective procedure is to apply a film of aluminium through a shadow mask so as to define a pattern. The aluminium is remo~able with dilute alkali such as sodium hydroxide. A
polyimide coating may also be used.
The resolution achievable is set by the extent of acid diffusion from under the trapping layer. This will be close .
~ 92/0~91 PCT/GB91/01421 _ 7 _ 20~
to the thickness of the layer o~ polymer. Typical resolutions are around lO0 nm.
In a further aspect, the present invention provides a waveguide structure comprising at least ~irst and second reqions formed in a semiconductive polymer so as to have different optical properties from one another, the optical properties having been selected to control the re~ractive index of each region. The present invention also provides an electroluminescent device including a layer of polymer comprising at least first and second regions formed in a semiconductive polymer so as to have different optical properties bandgaps from one another, the optical properties having been selected to control the wavelength of radiation emitted by each region.
The position of the bandgap in the polymer materials described controls the refractive index below the bandgap. To simplest order, the refractive index is inversely proportional to the bandgap. ~hus, patter~ing of the bandgap in the polymer layer permits the definition of structures in which there is a patterning of refractive index. By patterning the refractive index, fabrication of a wide range of quided-wave structures is enabled. In such s~ructures, a wave~lide is formed, for example; by a slab of high refractive index material - surrounded by regions of low refractive index material. Such waveguides may be used in a passive role, to route optical signal around a circuit, or in an active role in devices in which the electro-optical or optical propertie~ o~ the polymer are exploited. An example of such a device would be a laser diode with c~arge injection to form excited s~ates in the region o~ the wavequide.
A large-area bit-mapped display is one type of elec~roluminescent device which may be fabricated from the polymers of the present invention. In such displays the .: :
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W092/0~9l PCT/GB9l/014 ~ , - 8 - 2~
control of colour permitted by controlling the optical properties of the polymers allows fabrication of multicolour displays. In such an application, a resolution of some 10 microns or so is likely to be adequate and this is well within the capabili~y of the present invention.
Control of the optical properties of the copolymer may be achieved by varying the conversion conditions so that the conjugated copoly~er retains 50me of the modifier groups 50 as to`leavs saturated a proportion of the vinylic groups of the 10 copolymer. This has the effect of controlling the extent of conjugation of the copolymer so as to modulate the bandgap.
In this embodiment, the heating conditions are controlled so as to control the extent of elimination of the modifier group. Advantageously, the precursor polymer comprises a homopolymer, preferably a poly(para-phenylene-1,2-ethanediyl) polymer, a poly(2,5 dimethoxy paxa-phenylene-1,2-ethanediyl) polymer, or a poly(thienylene-1,2-ethanediyl) polymer.
Partial conversion of the precursor homopolymer yields a partially conjugated copolymer.
20 In a preferred embodiment, the semiconductive polymer comprises a conjugated poly(arylene vinylene) copolymer, wherein a proportion of the vinylic groups of the copolymer ?
are saturated by inclusion of a modifier group substantially stable to elimination during formation of the fil~, whereby the proportion o~ saturated vinylic groups controls the extent of conjugation, thareby modulating the semiconductor (~ -1r~ ~) ~andgap of the copolymer.
In this aspect o~ the invention, the pr6!cursor polymer . is formed whereby substantially all the leaviny groups are 30 replaced by the modifier groups. A suitable method for forming the pre-cursor polymer is to be found in Tokito et al Polymer (lg90), vol. 31, P.1137. By replacing the leaving group with a modifier group which is s~bstantially stable at .. . .
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ambient temperatures, a relatively robust precursor polymer is formed. Examples of typical modifier groups are set out in the following di~cussion. Advantageously the ~odifier group is an alkoxy group, prefarably a mPkhoxy group.
By controlling the extent of conversion to the copolymer, the extent of conjugation in the copolymer is controlled. Where the heating of the precursor polymer is carried out in the presence of acid this tends to result in conversion to the fully conjugated polymer. By controlling the temperature of heating and the time o~ heating it is possi~le to control the degree of conversion into the copolymer, thereby modulating the semiconductor bandgap of the copolymer. Thus, the wavelengths of radiation emitted during luminescence of the material may be selected by controlling the heating conditions. The more conversion to the conjugated copolymer, the more red-shifted the wavelength becomes. The colour of the emissions from blue to red can be controlled in this way.
Preferably, the temperature of heating is in the range 200 -~00C and preferably the heating time is up to 12 hours.
In a further embodiment, the precursor polymer comprises a poly(arylene-1,2-ethanediyl) precursor copolymer wherein a proportion of the ethane groups includ~! the modifier group substituent and at least some of the remaining ethane groups include a leaving group su~stituent, whereby elimination of the leaving group s~bstituen~s occurs upon heating substantially without elimination of the modifier group substituents so as to form the conjugated poly(arylene vinylene) copolymer.
The present invention u~ilizes the feature that the extent of -conjugation of conjugated poly(arylene vinylene) copolymers can be tailored by appropriate selection of the arylene constituents of the copolymer and of the modi~ier group. For example, phenylene moieties incorporating electron-donating . .
W092/0~91 - lO _ 2 0 8 9 ~ ~ ~ PCT/GB91/01421 substituent groups or arylene moieti~s with oxidation potentials lower in energy than that of phenylene are found to incorporate the modifier group preferentially as compared with the corresponding unsubstituted arylene moiety. Thus, the proportion of vinylic groups saturated by incorporation of the modifier group can be controlled by selection of the arylene moieties' substituents and the extent of conjugation of the copolymer may be concomitantly modulated. The extent of conjuyation of the copolymer affects the ~ -~ * bandgap o~ the copol`ymer. Therefore, selec~ion of appropriate reaction components may be used to modulate the bandgap in different regions of the polymer layer.
Thus, the invention contemplates a method of conversion of the precursor in~o its copolymer in which the extent of elimination of the leaving group constituents is controlled in different regions to control the colours of luminescence of the resulting copolymer film.
In a further aspect, there is proYided a method of forming a poly(arylene~ ethanediyl) precursor copolymer as defined above, which method comprises reacting a first monomer component with a second monomer component, in the presence of base and a solvenk comprising a modifier group, wherein the first monomer component comprises a first arylene moiety substituted with -C~2Ll and -C~2L2 and the second monomer component comprises a second arylene moiety subst tuted with -CH2~3 and -C~2L4, in which Ll, L , L and L each represents a leaving group substituent which may be the same or different from one another. This method may constitute a first step in the formation of a partially conjugated poly(arylene vinylene) copolymer.
A function o~ the modifier group is to interrupt the conjugation of the poly(arylene vinylene) copolymer by .,. . ~ , . - -' ~" ; , ~ ' , ' ~, ' .
~ 92/0~91 PCT/GB91/01421 2089~8 ~
saturation of the vinylic groups o~ the copolymer chain.
Thus, for the modifier group to be successful in this ~unction it must be relatively stable to elimination during formation of the poly(arylene vinylene) copolymer. Typical modifier groups include:
RO-, RS-, ArO-, ArS-, NC-, R-S-, R-S-, RSe-, HO-.
A preferred modifier group is a Cl to C6 alkoxy group, more preferably a methoxy group.
The poly(arylene-1,2-ethanediyl) precursor copolymer may be 10 formed in a first step by reacting a first monomer component with a second monomer component, in the presence of base and a solvent comprising the modifier group, wherein the first monomer component comprises a first arylene moiety substituted with ~CH2L1 and -CH2L2 and ~he second monomer component comprises a second arylene moiety substikuted with -CH2L3 and -C~2L4, in which Ll, L2, L3 and L4 t each represents a leaving group substituent which may be the same or di~`erent from one ~nother.
In the step of forming the poly(arylene-1,2-ethanediyl) 20 precursor copolymer the solvent preferably also includes water, Thus, for agueous solvents, the modifier group must be present as a water-miscible polar solvent/reagent. Where the modifier group is alkoxy, the corresponding sol~ent or solvent component would therefore be an alcohol. Pre~erably the solvent comprises at least 30~ modifier group by weight. More pre~erably the sol~ent is water: methanol at a ratio of 1:1.
Modifier groups may be introduced selectively either during formation of the precursor copolymer or by displacement reactions on the precursor copolymer.
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The identity of the leaving groups is not particularly critical provided that the first and second monomer components may react together in the presence of base and provided that the leaving group substituents on the poly(arylene l,2-ethanediyl) precursor copolymer may eliminate upon heating.
Typical leaving groups include 'onium salts in general, bearing a non-basic counter anion. Sulphonium salts, halides, sulphonates, phosphates or esters are suitable.
Preferably a sulphcnium salt such as a tetrahydrothiophenium salt is used.
Throughout this specification the term arylene is intended to include in its scope all types of arylenes including heteroarylenes as well as arylenes incorporating more than one ring structure, including fused ring structures.
At least two arylene moieties are present in the copolymer chain and these may be substituted or unsubstituted arylene or heteroarylene moieties. Suitable substituents include alkyl, O-alkyl, S-alkyl, O-aryl, S-aryl, halogen, alkyl sulphonyl and aryl sulphonyl. Preferred substituents include methyl, methoxy, methyl sulphonyl and bromo, and the arylenes should preferably be substituted symmetrically. In a more preferred em~odiment of the invention, one of th~! arylene moieties of the copolymer is unsubstituted and comprises para-phenylene.
Preferably, the second component is selected from the group comprising 2,5-dimethoxy-para-phenylene, 2,5-thienylene and ~,5-dimethyl-para-phenylene. Nore preferably the para~phenylene moiety is present in the copolymer chain in an amount re~ulting from conversion of a precursor copolymer ~ -formed by reaction of at least 70 mole % of the PPV precursor monomer unit.
Referring in particular to the method of forming the conjugated polyarylene vinylene copalymer, this is effected by heating, pre~erably in a temperature range of 70-300C. The :. . . . .
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heating is performed substantially in the a~sence of oxygen, for example under an inert atmosphere such as that of one or more in~rt gases or under vacuum.
In the step of forming the precursor copolymer, a range of reaction temperatures and reaction times is possible. ~he reaction temperature is constrained mainly by the temperature range at which the solvent is liquid and typically varies from -30C to +70C, prefera~ly -30C to l30C, more preferably -5C to ~10C. The reaction time may typically be between l minu~e and l day, depending on the temperature and reaction components, pre~erably not greater than 4 hours.
Once the precursor copolymer is formed this may optionally be purified, for example by precipitation witA a salt o~ a non-nucleophilic counter anion (i.e. anion exchange).
Prefera~ly the precursor copolymer is dialysed against an appropriate solvent such as water or a water-alcohol mixtureO
Choice of the base used in the reaction is not particularly critical provided that it is soluble in the solvent. Typical bases include hydroxides or alkoxide derivati;~s of Group I/II
20 metals and may be present at a ratio of 0.7-l.3 mole equivalents of base per mole of monomer,, Prererably, hydroxides of lithium, sodium or potassium are used in equimolar proportions with the monomer.
In a further embodimen~, at least one o~ the monomer units of the copolymer comprises an arylene vinylene unit substituted with a solubilizing group in the arylene ring so as to render the copolymer soluble. Any known solubilizing group may be used for this purpose. Where the copolymer is to be solu~le in wate~, a charged solubilizing group is preferred. The 30solubilizing yroup typically comprises an alkoxy group of at least 4 carbon atoms~ The alkoxy group may be branched or linear and preferably introduces asymmetry into the arylene rings so as to disrup~ the packing of the copolymer chains.
- 14 - 2~9~
Preferably the alkoxy group is a 2-methylpentyloxy or a 2-ethylhexyloxy group. A urther alkoxy group such as a methoxy group may be substituted para to the solubilizing group.
By making the copolymer soluble, this confers the a~vantage of allowing the copolymer to be processed in solution.
In the following when reference is made to ratios of P~V, dimethoxy-PPV, PTY and dimethyl-PPV monomer units in bath precursor and conjugated copolymer structures the ratias are defined by the amounts of the corresponding monomer units us~d in the initial polymerisation reaction.
For a better understanding of the pres2nt invention and to show how the same may be carried into effect, reference will now be made by way of example to the accompanying drawings.
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W092/0~91 PCT/GB91/01421 - 16 2 0 ~ 9 ~
BRIE~ DESCRIPTION OF THE DRAWINGS
Figure l is a diagram showing an example of the steps of a method for producing the copolymers prepared via a soluble precursor;
Figure 2a is a graph showing the absorption spectra of spin-coated thin films of PPV and copolymers of PPV, as the majority constituent, and dimethoxy-PPV (DMeOPPV) as converted at ~20C in vacuo for 2 hours Curve a is PPV homopolymer Curve b is 95% PPV to 5%DMeOPPV
Curve c is 90% PPV to 10% DMeOPPV
Curve d is 85% PPV to 15% D~eOPPV
Curve e is 80% PPV to 20~ DMeOPPV
Curve f is 70% PPV to 30% DMeOPPV
Figure 2b is a graph showing the absorption spectrum of a spin-coated thin film of dimethoxy-PPV as converted at 220C
in the present of acid for two hours. ~-Figures 3a and 3b are graphs showing respectively the emi,ssion spectra for thin spin coated and thick solution cast ;
~ilms of a copolymer produced from a l:9 molar ratio of dimethoxy-PPV and PPV monomer units respectively, converted at 220C in vacuo for two hours; - ~;
Figures ~a and 4b are graphs showing respectively the emission spectra for thin spin coated and thick solution cast films of a copolymer produced from a 1:4 molar ratio of dimethoxy PPV and PPV monomer units respectively, converted at 220C in vacuo for two hours;
Figures 5a and 5b are graphs showing respectively the photoluminescence spectra for homopolymers of PPV and dimethoxy PPV;
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w--j2/0~1 PCTiGB91/01421 - 17 ~ 2 ~9 4 ~1 Figures 6a, b and c are graphs showlng respectively the absorption spectra of a homopolymer of PPV, and random copolymers of PPV and PTV produced respectively from l9;1 and 9:1 molar ratios of PPV and PTV monomer units, converted at 220C in vacuo for two hours, Figures 7a, b and c are graphs showing respectively the photoluminescence emission spectra for thick free cast films of a homopolymer of PPY; a copolymer produced from a 19:1 molar ratio of PPV and PTV monomer units respectively; and a copolymer produced from a 9:1 molar ratio of PPV and PTV
monomer units respectively;
Figures 8a, b and c are graphs showing the absorption spectra of spin-coated thin films of a homopolymer of PPV, and random copolymers of PPV and dimethyl PPV produced respectively from 19;1 and 9:1 molar ratios of PPV and PTV dimethyl monomer units as converted at 220C in vacuo for two hours;
Figures 9a, b and c are graphs showing re~spectively the photoluminescence emission spectra of thlck free cast films for the homopolymer of PPV; a copolymer produced from a 19:1 20 molar ratio of PPV and dimethyl PPV monomer units respectively; and a copolymer produced ~rom a 9:1 molar ratio of PPV and dimethyl-PPV monomer units re~;pectively;
Figures lOa, lla and 12a are graphs showing the current/voltage characteristics of a thin film of respectively PPV; a copolymer produced ~rom a 9:1 molar ratio of PPY and dime~hoxy PPV monomer units respectively; and a copolymer -produced from a 9:1 molar ratio of PPV and thienylene vinylene monomer units respectively, the polymer films baing spin-coated and converted at 220C ~or two hours in vacuo :
with hole injecting electrodes of oxidised aluminium, and with electron injecting electrodes of aLuminium;
W092/03491 PCT/GB91/0142Y~--18 - 2~89~8~
Figures 10b, llb and 12h are graphs showing the luminescence/current relationship for a thin film of respectively PPV; a copolymer produced from a 9:1 molar ratio of PPV and dimethoxy PPV monomer units respectively; and a copolymer produced from a 9:1 molar ratio of PPV and thienylene vinylene monomer units respectively, the polymer films being spin~coated and converted at 220C ~or two hours in vacuo with hole injecting electrodes of oxidised aluminium, and with electron injecting electrodes of aluminium;
Figure 13 illustrates the electroluminescent quantum yield of random copolymers formed from PPV and dimethoxy-PPV monomer units as measured in thin film structures with hole injecting electrodes of oxidised aluminium, a spin-coated film converted at 220C in vacuo for two hours, and with electron injecting electrodes of aluminium;
Figure 14 illustrates the electroluminescent quantum yield of ~:~
random copolymers formed from PPV and P~ monomer units as measured in thin film structures with hole injecting electrodes of oxidised aluminium, a spin-coated film converted at 220C in vacuo for two hours, and wit:h electron injecting electrodes of aluminium;
Figure 15 illustrates the electroluminescent quantum yield of random copolymers formed from PPV and dimethyl-PPV monomer units as measured in thin film structures with hole injecting ; .
electrodes of oxidised aluminium, a spin-coated film converted at 220C in vacuo ~or ~wo hours, and with electron injecting electrodes of aluminium;
A film of copolymer of 10% DMeOPPV: 90% PPV was spin-coated and an area was capped with 500A of evaporated aluminium. The sample was then thermally converted for 12 hours at 220C in vacuo. The aluminium capping layer was ~.`.-92/0~91 - 19 _ 2 0 8 9 ~ 8 ~ PCT/~B91/0l421 removed by reacting it in dilute alkali. Figures 16 and 17 show the optical absorption spe~tra and photoluminescent spectra for two areas in a polymer ~ilm which have undergone different conversion treatments;
Fiqures 18a, 18b, 18c are graphs showing the infrared spectra of precursor to random copolymers of PPV and MMP-PPV(2-methoxy -5-(2'-methylpentyloxy)-PPV produced from 80 : 20, 90 : 10, and 95 : 5 w/w ratios of PPV and MMP-PPV monomer units, resp`ectively;
Figure l9a, l9b, 19c, 19d, are graphs showing the absorption spectra of spin-coated thin films of random copolymers of PPV
and MMP-PPV produced from 80 : 20, 90 : 10, and 95 : 5 and 100 : O w/w ratios of PPV and M~P-PPV monomer units, respectively as converted at 220C in vacuo for 12 hours;
Figure 20 is a graph showing the current/voltage characteristics of a thin film of a random copolymer of PPV
and MMP-PPV produced from 90 : 10 w/w ratio of PPV and MMP-PPV
monomer units as converted in vacuo at 220C for 12 hours on a substrate of IT0-coated glass and with calcium as a cathode;
Figure 21 is a graph showing the luminance/current characteristics of a thin film of a random copolymer of. PPV
and ~MP-PPV produced ~rom 90 ~ 10 w/w ratio of PPV and MMP-PPV
monomer units as converted in vacuo at 220c for 12 hours on a substrate of IT0-coated glass and wi~h calcium as a cathode;
Figures 22a and 22b are graphs showing the infrared spectra of precursors of random copolymers o~ PPV and M~H-PPV
(2-methoxy-~-(2'-ethylhexyloxy)-PPV produced from 90 : 10 and 95 : 5 w/w ratios o~ PPV and MEH PPV
(2-methoxy-5-(2'-ethlyhexyloxy)-PPV) monomer units respectively;
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W092/0~91 2 0 8 ~ PCT/GB91/0142 ~ .
Figures 23a, 23b, 23c, 23d are graphs showing the absorption spectra of spin-coated thin films of random copolymers of PPV
and MEH-PPV produced from 80 : 20, 90 : lO, 95 : 5 and lO0 : o -~
w/w ratios of PPV and MEH-PPV monomer units, respectively as converted at 220C in vacuo for 12 hours;
Figure 24 is a lH NMR spectrum of the copolymer described in example ll produced from 5 : 95 w/w ratio of PPV and MEH-PPV
Figures 25a, 25b, 25c are graphs showing the infrared spectra of (c) MEH-PPV and of random copolymers of PPV and ME~-PPV
produced from (a) 20 : 80 and (b) 5 : 95 w/w ratios of PPV and MEH-PPV monomer units, respectively, ~y the method described in example ll;
Figure 26 is a graph showing the absorption spectra of spin-coated thin films of MEH-PPV and of random copolymers of PPV and MEH-PPV produced from 20 : 80 and 5 : 95 w/w ratios of PPV and ME~-PPV monomer units, respectively;
Figures 27a and 27~ are graphs showing t:he photoluminescence emission spectra of random copolymers o~ PPV and MæH-PPV
produced from 20 : 80 and 5 : 95 w/w rat:ios of PPV and MæH-PPV
monomer units, respectively;
Figures 28a and 28b are graphs showing the electroluminescence spectra for random copolymers o~ PPV and MEH-PPV produced from ~;~
20 : 80 and 5 : 95 w/w ratios of PPV and ~EH-PPV monomer units, respectively;
Figures 29a and 29b are graphs showing the current/voltage ~
characteristics and luminance/voltage relationship for a thin ~:
film of a random copolymer of PPV and MEH-PPV produced from 20 : 80 w/w ratio of PPV and MEH-PPV monomer units thin; films were spin-coated onto substates of IT0 coated glass and :
aluminium cathodes were evaporated on top, . .
Y. ~92~0~91 PCTJGB9t/01421 - 21 - ~ 2 ~ ~ 9 ~ 8 ~
Figures 30a and 30b are graphs showing the current/voltage characteristics and luminance/voltage relationship for a thin r lm of random copolymer of PPV and MEH-PPV produced from 5 :
95 w/w ratio of PPV and ME~-PPV monomer units: thin films were , spin-coated onto substates of ITO coated glass and ~luminium cathodes were evaporated on top;
Figure 3l is a scatter graph showing the quantum yield of random copolymers formed from PPV and MMP-PPV monomer units as measured in thin film structures with hole injecting electrodes of oxidised aluminium, a spin-coated film converted at 220C in vacuo for 12 hours, and with electron injecting electrodes of aluminium;
Figure 3la is a graph showing the photoluminescence spectra of MEH-PPV and random copolymers of (a) MæH-PPV and PPV produced from (b) 95 : 5 and (c) 80 : 20 w/w ratios of MEH-PPV and PPV
monomer units, respectively;
Figures 32 (a to d) show respectively the formal structural formulae of: the THT-leaving PPV precursor; the MeO-leaving PPV precursor; PPV; and partially converted MeO-leaving PPV;
Figure 33 is a graph showing the absorption spectra of precursors of THT-leaving PPV (broken) and MeO-leaving PPV
Figure 34 is a graph showing the absorption spectra o~
THT-leaving PPV (broken) and MeO-leaVing PPV (solid) after thermal conversion at 300C for 12 hours in vacuo;
Figure 35 is a graph showing the absorption spectra of thin spin-coated films of MeO-leaving PPV before (dotted) and after (solid) thermal conversion at 300C for 12 hours in vacuo:
... . .
W092/0~91 - 22 -.~ ~ 9 ~ ~ ~ PCT/GB91/01421~. .
Figures 36 (a) and (b) are graphs show:ing respectively thP
current-voltage and l~inance-current characteristics of THT~leaving PPV as converted in vacuo at 220 for 12 hours on a substrate of TTO-coated ylass and with aluminium as a cathode;
Figures 37 (a) and (b~ are graphs showing respectively the current-voltage and luminance-current characteristics of MeO-leaving PPV as converte~ in vacuo at 300 for 12 hours on a substrate of ITO-coated glass and with aluminium as a cathode;
Figure 38 is a graph showing the electroluminescence emission spectra of THT-leaving PPV (dotted) and MeO-leaving PPV
(solid) after thermal con~ersion;
Figures 3~(a) to (c) show respectively the formal structural formulae of the random copolymers of: PPV and DMeOPPV in precursor form; as converted thermally ln vzcuo; and as convPrted thermally in the presence of acid;
Fiqure 40 is a graph showing the absorption spectra of spin-coated thin films of random copol~mers of PPV and DMeOPPV
: 20 after thermal conversion as converted in vacuo at 220C for 12 hours. The percentages on the figure represent the percentage of DMeOPPV ~onomer units w/w from which the precursor was formed;
Figure 4l is a graph showing the infra red absorption spectra of a 20% random copolymer of DMeOPPV and PPV in which:
Figure 4la is the precursor Figure 4lb is the copolymer spin-coated on KBr and converted at 220 in vacuo for two hours Figure 41c is the same sample further converted for two hours 30 at 220C in the presence of acid;
: : . i .
- ', ' ~ ' , , ~;~J2/0~9l - 23 _ 2 D 8 9 4 ~ ~ Pcr/GB9l/0l42]
Figures 42a, 42b, 42c, ~2d, 42e, are graphs showing rPspectively the lnfrared a~sorption spectra of PPV and the random copolymers of PPV, as the major constituent, and DMeOPPV produced from 95 : 5, 90 : 10, 80 : 20 and 70 : 30 molar ratios of PPV and DMeOPPV monomer units respectively;
Figure 43 is a graph showing the absorption spectra o~
spin-coated thin films of a 20~ random copolymer of DMeOPPV
and PPV converted ~a vacuo (a,b) and in the presence of HCl (c,d);
Figure 44 is a graph showing the variation of bandgap with different conversion conditions; the higher bandgap material (a) converted for 2 hours at 220C in vacuo, the lower bandgap material (b) converted for 12 hours at 100C in vacuo and subsequently four hours at 220C in a 15% random copolymer of DMeOPPV and PPV;
Figure 45 is a graph showing the photoluminescence spectra of a 30% random copolymer of D~eOPPV and PPV;
Figure 46 is a graph showing the photoluminescence emision spectra of a 30% random copolymer of DMeOPPV and PPV;
Figure 47 is a graph showing tha absorption spectra of capped and uncapped 10% random copolymers of DMeOPPV and PPV; and Figure 48 is a graph showing the photoluminescence e~ission spectra of capped and uncapped 10% random copolymers of DMeOPPV and PPV after thermal conversion.
In each of Figures 45 to 48, a film of copolymer were spin-coated and an area was capped with 500A of evaporated aluminium. The sample was then thermally convertPd for 12 hours at 2~0C in vacuo. The aluminium capping layer was removed by dissolving it in dilute alkali. The lower energy -~
absorption and photoluminescanca spectra are from the capped regions of polymer.
: ' : - , ' : . .
~ ,' ' ':, ' .
~ - ': : -:
W092t0~91 - 24 _ 2 0 ~ 9 ~ 8 .J pcr/~B9l/ol4~ ~
DESCRI~TION OF T~ EE~ _ M~ODI~ NTS
Figure 1 illustrates in general terms a process for producing copolymers according to one embodiment of the inventionO A
mixture of two monomeric ~is-sulphonium salts in a suitable solvent was polymerised by reaction with a base. The resultant soluble precursor copolymer was p~rified and then converted to a conjùgated form by heat treatment.
Examples of both the precursor copolymers and the partially conjugated copolymers are shown in the foregoing formulae drawings. The compound of General Formula I represents a precursor copolymer of the compound of General Formula II, which is a poly(para-phenylene vinylene-co-2,s-di5ub5tituted-para phenylene vinylene) copolymer. Similarly, the compound of General Formula III
~, represents a precursor copolymer of the compound of General Formula IV, which is a poly(2,5-thienylene vinylene-co-disubstituted-para-phenylene vinylene) copolymer.
In these compounds the extent of conjucJations will be determined by the values of n,m,o and p. Clearly, for a 20 partially conjugated copolymer (II) or (IV), o-~p > 1, and so at least some of the vinylic groups will be saturated by inclusion o~ the modifier group repres~!nted by -OR'.
The present invention is concerned in one aspect with improving the efficiency of radiative decay of excitons by trapping them on local regions of the polymer chain, which have lower energy gaps and thus are rPgions of lower potential energy for the excitons, so that the excitons are confined for a long enough period that they will decay radiatively. This nas been achieved by the-synthesis of a family of copolymers in which the units which make up the polymer chain are selected from two or more chemically different groups, which ' ~i 32/0~91 2 0 ~3 9 ~ ~ ~ PCT~GBgl/01421 - 2; -?ossess differing bandgaps in their respective homopolymers.
Such Dolymers have been synthesised while s~ill retaining all the desirable processing and materials properties of PPV. In the examples shown in this disclosure, para-phenylene vinylene is used as one of the components (usually the majority component) to~ether with varying compositions of the ~ollowing o~her components or their unconverted precursors, as discussed more fully below: OCH3.
2,5-dimethoxy-para-phenylene vinylene ~ CH_CH-(PD~OPV) 2,5-thienylene vinylene/5 3 CH-CH-( P~V) CH
J/ \ CH-CH-2,~-dimethyl-para-phenylene vinylene \~/
(PDMPV) H3C/ CH3 ~ `
, O-cH2-cH-cH2-cH2-cH3 2-methoxy-5-(2'-methylpentyloxy) ~// \~ CH=CH--para-phenylene ~rinyleneH3CO CH2-CH3 t~IP-PPV) ~ , ~ OCH~7-CH-(CH2)3-CH3 2-methoxy-5-(2'ethylhexyloxy)para ~ CH=CH---phenylenevinylene H3CO
(MEH-PPV) ~ ;
. ~., SVBSTI ' VTiE~ S~IE~T
... . . ..
- ~ . ' . : - , :.
, . .
. . .. ; ....
WO92/0~91 PCT~GB91/01421~-- 26 2~9l~
The first three of these components are available in the form of their correspanding homopolymers, and the first two possess an energy gap lower than that of PPV. PPV shows the onset of ~to~* optical transitions at 2.5 eV; poly(2,5-dimethoxy-para-phenylene vinylene), P~MOPV, at 2.1 eV and poly(2,5-thienylene vinylene), PTY, at 1.8 eV. It is expected, on the basis of the known inductive effects of its substituents, that poly(2,5-dimethyl-para-phenylene vinylene~, PDMPV, will have a bandgap a little lower than that of PPV.
Dimethyl PPV (DMPPV) has a higher bandgap in its homopolymer than does PPV. This is contrary to the argument which runs that the methyl substi~uents have inductive effects and so will lower the bandgap of DMPPV over PPV. The true picture is that due ~o the steric interaction of the dimethyl groups, the polymer conjugated backbone is distorted decreasing the degree of electron delocalisation along the bac~one and thus raising the bandgap with respect to PPV. This is evidenced in electron diffraction studies and quantum chemical calculations Thus, the copolymers of PPV and DimethylPPV as prepared via a THT leaving group (Figure 8) have a cont:rolled shift in band~ap ~ot because ~he DMPPV units are saturated ~iving a copolymer of saturated and unsaturated units but because DMPPV and P~V have genuinely different bandgaps and we are forming a copolymer of the two. We evidence that there are no saturated units by an a~cence of 1094cm l stretch in the F~I~ spectra of the precursors. Bandgap is still controllable hence by selection of ~he monomer units ratio.
There follows specific examples o~ process~s i~ accordance with em~odiments of the invention.
WO92/0~91 PCT/GB91/014~1 - 272989~
E~xamDle 1 ~ A mixture of ~ bis(tetrahydrothiophenium chloride)-p-xylene `
(0.97 g, 2.8 mmol) and ~ bis(tetrahydrothiophenium chloride)-2,5-dimethoxy-p-xylene (0.12 g, 0.3 mmol) in methanol (7.1 ml) was deoxygenated with nitrogen and cooled with an ice-bath. A nitrogen deoxygenated aqueous sodium hydroxide solution (0.4 M, 2.9 mmol, 7~1 ml) was added dropwise and the reaction mixture was left to stir ~or 1 hour at 0C under inert atmosphere. The reaction was terminated n by addition o~ hydrochlor-c acid (0.4 M, l.O ml). The viscous solution was then dialyzed against deoxygenated distilled water (3 x lOOO ml) over 3 days using cellulose membrane dialysis tubing with a molecul~r weight cut~o~f of 12,400 (supplied by Sigma Chemical Company Limited, Dorset, U.R.).
The solvent was completely removed in vacuo at room temperature from the material remaining in the dialysis tubing. The residue was dissolved in dry methanol (15 ml).
:' . . . . . . ..
W092/0~91 2 0 8 ~ 4 8 ~ PCT/GB91/0142 - 2~ -Exam~le 2 A mixture of d,~ bis(tetrahydrothiophenium chloride)-p-xylene (0.91 g, 2.6 mmol) and ~,~'-bis(tetrahydrothlophenium chloride)-2,S dimethyl-p-xylene (0.10 g, 0.26 mmol) in methanol (9.S ml) was deoxygenated with nitrogen and cooled with an ice-bath. A nitrogen deoxygenated ice-cold aqueous sodium hydroxide solution (0.4 M, 2.9 mmol, 7.1 ml) was added dropwise and the reaction mixture was left to stir for 1 hour at 0C under inert atmosphere. The reaction was terminated by addition of hydrochloric acid (0.4 M, 0.5 ml). The viscous solution was then dialyzed against deoxygenated distilled water (3 x 1000 ml) over 4 days using cellulose membrane dialysis tubing with a molecular weight cut-off of 12,400 (supplied by Siqma Chemical Company Limited, Dorset, U.K.).
The solvent was completely removed in vacuo at room temperature from the material remaining in the dialysis tubing. The resid~e was dissolved in dry methanol (10 ml).
Example 3 A mixture of ~ ~'-bis(tetrahydro~hiophenium chloride)-p-xylene (0.98 g, 2.8 mmol) and ~,d'-bis(tetrahydrothiophenium chloride)-2-nitro-p-xylene (0.11 g, 0.33 mmol) in methanol (8.0 ml) was deoxygenated with nitrogen and cooled with an ice-bath. A nitrogen deoxygenated ice-cold aqueous sodium hydroxide solution (0.4 ~ r 2.9 mmol, 8.0 ml) was added rapidly and the reaction mixture was left to stir for 3.5 hours at 0C under inert atmosphere. The reaction was terminated by addition of hydrochloric acid (0.4 M, 1.0 ml). The viscous solution was then dialyzed against deoxygenated distilled water (3 x 1000 ml) over 4 days using cellulose membrane 30 dialysis tubing with a molecular weight cut-off of 12,400 (supplied by Sigma Chemical Company Limited, Dorset, U.X.).
The solvent was completely removed in vacuo at room ~-. - , : . .
:'' ` ' ; : . ,. . ,~ '. .
' ~: ;- ~ , ;
. - '.
~ 92/0~91 2 0 ~3 9 ~ 8 1 PCT/&B91/01421 temperature from the material remaining in the dialysis tubing. The residue was dissolved in dry methanol (4 ml).
E a~le _4 : Preparation of ~ et~oxy~4-(2"-methYl~entylo w benzene Sodium metal (6.9g g, 304 mmol) was dis501ved in dry methanol (120 ml) under Ar to give a 2.5 M solution of sodium m~thoxide. A solution of 4-methoxyphenol (31.4 g, 253 ~mol) in dry methanol (150 ml) was added and this mixture was heated to reflux for 30 min. After cooling to room temperature, a 0 solution of 1-~romo-2-methylpentane (46.0 g, 279 mmol) in dry methanol (100 ml) was added. The mixture was then heated to raflux for 16 hours. The solvent was removed in_yDgy~, the residue dissolved in ether (200 ml), washed with dilute aqueous sodium hydroxide (250 ml) and water (500 ml), dried over MgS04 and concentrated in vacuo again. Distillation at 80C/0.5 mm Hg afforded 14.0g (27~) l-methoxy-4-(2'-methylpentyloxy)benzene, lH NMR (250.1 MHz, CDC13):~ = 0.94(t,3 H), 1.02 (d, 3 H), 1.16 - 1.56 (m, 4 H~, 1.93 (m, 1 H~, 3.64 - 3.82 (m, 2 H), 3.77 (s, 3 H), 6.81 -20 6.89 (m, 4 H), C NMR (100.6 MHz, CDC13):~ = 14.3, 17.0 (both CH3), 20.1, 35.8 (both CX2), 33.0 (CH), 55.7 (OCH3), 73.9 (0CH2), 11~.6, 115.4 (aromr CHj, 153.5, 153.6 ( e~ C). I~(fil~) o 2956(m), 1509(s), 1232(5), 1045(m), 824(m) cm 1, MS(EI) : m/z (%) = 208 (100), 124 (32), Calcd.
for cl3H20O2 : C 74.96, H 9.68 found : C 7S.03, H 9.70.
Exam~le 5. Pre~araton o~_l,4-bis(chloromethYl)-2-methoXV-5-; - (2' meth~l~entyloxy~L~enzene A mixture of hydrochloric acid (37%, 59 ml), formaldehyde (39%, 35 ml), l-methoxy-4-(2~-methylpentyloxy)benzene (14.0 g, - 30 67.4 mmol) and dioxane (100 ml) was saturated with hydrogen chloride for 15 min at 0,C and stirred for 1.5 hours at room -~
WOs~t0~l PC~/&B9l/0l42l~-_ 30 _ 2 ~ 8 ~
temperature. Another 30 ml of formaldehyde was then added at 0C and hydrogen chloride was bubbled through the reaction mixture for 10 min. After stirring for 16.5 hours at room temperature, the mixture was heated to reflux for 4 hours.
The solvents were then completely removed to give a colourless solid residue which was dissolved in a minimum amount of hot hexane (50 ml). Thi~ solution was poured into ice-cold methanol (300 ml). The precipitate was filtered under suction and dried to afford 15.5 g (75%) of 1,4-bis(chloromethyl)-2-methoxy-5-(2'-methylpentyloxy)benzene, m.p. 78 ~ 80C. lH NMR (250.1 MHz, CDCl3) : S = 0-92( t, 3 H), 1.04 (d, 3 H), 1.22 - 1.55 (m, 4 H), 1.95 - 2.05 (m, 1 H), 3.73 - 3.90 (m, 2 H), 3.85 (s, 3 H), 4.62 (s, 2 H), 4.64 (s, 2 H), 6.89 (s, l H), 6.92 (s, l H) 13C NMR (100.6 MHz, CDCl3 ) : ~ = 14.3, 17.1 (both CH3 ), 20.0, 35.7 (both CH2), 33.0 (CH), 41.3, 41.4 (both ~; CH2Cl), 56.3 (OCH3), 73.9 (OC~2) 113.3, 114.1 (arom.
C~), 126.8, 127.0, 150.8, 150.9 (i~so C). IR (~Br) : 2g58 (m), 1517 (s), 1466 (m), 1414 (s), 1263 (s), 1230 (s), 1036 ~; 20 (s), 734 (s), 6g6 (s) cm 1. MS(EI) : m/z (%) = 304 (18), 220 (38), 84 (41). Calcd- for C15H22Cl22 C 59-02~ H
` 7.26; ~ound : C 58.14, H 6.97.
Example_6: PreParation o~ ~ ~ bis(tetrahYdrothio~henium ; chloride~2-methoxy~5~(2'-methyl~ent~loxy)-p-x~lene Tetrahydrothiophene (20.9 ml, 237 mmol) was added to a suspension of 1,4-bis(chloromethyl)-2-methoxy-5-(2'-methylpentyloxy)benzene(14 .5 g, 47.3 mmol) in dry methanol (200 ml). The solid dissolved to form a clear solution within 10 min. This solution was then heated to 50C for 17 hours. The solvent was completely removed in vacuo, the residue treated with dry acetone, then filtered under suction and dried to give 12.7 g (56%) of ~ bis(tetrahydrothiophenium chloride)-2-methoxy-:~ 5-(2'-methylpentyloxy)-p-xylene. lH NMR (250.1 ~Hz, CD30D) =0.97(t, 3 H), 1.10 (d, 3 H), 1.26 - 1.61 (m, 4 H), 2.04 (m, 1 H), 2.23 - 2.53 (m, 8 H), 3.55 (br. m, 8 H), ' , , :
: . :
~,9~/0~91 PCr/GB91/01421 - 31 - 2 ~ 8 9 ~ 8 ~
3.a6 - 4.05 (m, 2 H~, 3.97 (s, 3 H), 4.56 (s, 2 H), 4.57 ~s, 2 H), 7.35 (s, 1 H), 7.37 (s, 1 H). 13C NMR (100.6 MHz, CD30D) : ~ - 14.7, 17.5 (CH3), 21.1, 29.7, 29.8, 34.3 - (CH2), 36.9 (CH), 43.1, 43.2, 44.5, 44.6, 44.8 (CH2), 57.1 (OCH3), 75.8 (OC~2), 116.5, 117.3 (arom. CH), 121.3, 121.6, 153.0, 153.3 (i~so C). IR (~3r) : 2953 (s), 1514 (s), 1404 (s), 123~ (s), 1033 (s) cm 1.
Example 7 A mixture of d~ bis(tetrahydrothiophenium chloride)-~
-xylene (0.9o g, 2.6 mmol) and ~ bis(tetrahydrothiophenium chloride)-2-methoxy-s-(z'-methylpentyloxy)-~-xylene (o.10 g, O.21 mmol) in methanol (10 ml) was deoxygenated with argon and cooled with an ic:e-bath. An argon deoxygenated ica-cold aqueous sodium hydroxide solution (0.4 M, 2.6 mmol, 6.9 ml) was added dropwise and the reaction mixture was left to stir for 1 hour at 0C under inert atmosphere. The reaction was terminated by addition of hydrochloric acid (0.4 M, 3.0 ml).
The viscous solution was then dialyzed against deoxygenated distilled water (3 x 2000 ml) over 3 days using cellulose membrane dialysis ~ubing with a molecular weight cut-of~ of 12,400 (supplied by Sigma Chemical Company Ltd., Dors~t, U.K.). The solvent was completely remo~ed in vacuo at room tempera~ure from the material remaining in the dialysis tubing. The residue was dissolved in dry methanol (20 ml).
IR spec~ra of copolymers: Figure 18.
Exam~le 8 _Preparation of ~-methoxv 4-L2'-ethYlhexYloxy)benzene Sodium metal (6.50 g, 2~3 mmol~ was dissolved in dry methanol ' (100 ml) under Ar to give a 2.5 ~ solution of sodium methoxide. A solution of 4-methoxyphenol (29.3 g, 236 mmol) in dry methanol (lS0 ml) was'added and this mixture was heated ~ to reflux for 30 min. After cooling to room temperature, a :' i .,~-. .
: . .. .
: : - . :~ . . : . . ' . . '; ' ,: .
- 32 _ 2 ~8~ 4 ~1 solution of 1-bromo-2-ethylhexane (46.5 g, 259 mmol) in dry methanol (150 ml) was added dropwise. The mixture was then heated to reflux for 18 hours. The solvent was removed in vacuo, the residue dissolved in ether ~200 ml), washed with dilute aqueous sodium hydroxide (500 ml) and water (500 ml), dried over ~gS04 and concentrated in vacuo again.
Distillation at 120C~0.1 mm Hg afforded 24.2 g (43%) 1-methoxy-4-(2'-ethylhexyloxy)benzane.
Example 9: Preparation of 1 4-bis(chlo~omekhYl~-2-methoxv-5-(2~-ethylhexyloxy)~enzene A mixture of hydrochloric acid (37%, so ml), formaldehyde (39%, 70 ml), 1~methoxy-4-(2~-ethylheXyloxy)benzene (24.2 g, 101 mmol) and dioxane (120 ml) was saturated with hydrogen chloride for 20 min at 0C and stirred for 3 hours at room temperature. Another 50 ml of formaldehyde was then added at 0C and hydrogen chloride was bubbled through the mixture for 10 min. After stirring for 3 days at room temperature, the mixture was heated to reflux ~or 3.5 hours. The solvents were then completely removed to give a pale yellow solid residue which was dissolved in a minimum of hot hexane (75 ml).
This solution was poured into ice-cold methanol (300ml). The precipitate was filtered under suction, washed with methanol (200 ml) and dried to afford 21.7 g (63%) of 1,4-bis (chloromethyl)-2-methoxy-5-(2'-ethylhexyloxy)~enzene, m. p. 58 ~ 60C. From the mother liquor was obtained another 5.48 g (16~) of bis(chloromethyl)-2-methoxy-~-(2'-ethylhexyloxy)benzene, m. p.
53 - 55C. H NMR (250.1 ~Hz, CDC13) : ~
= 0.85 - 0.96 (m, 6 H), 1.26 - 1.7S (m, 9 H), 3.74 - 3.86 (m, 2 H), 3.83 (s, 3 H), 4.06 (s, 4 H), 6.89 (s, 1 H), 6.90 (s, lH). IR (K~r) : 2924 (m), 1516 (s), 1466 (m), 1415 (s), 1263 (s3, 1227 (s), 1182 (m), 1032 (s), 733 (m), 700 (s), 614 cm~1 (m) , : :-':~ .' ' .:'~ ' ' , ~ .. . .
:~,'' . ` ' `
: . .
~ -J2/0~91 _ 33 _ 2 ~ 8 9 4Q~-~ PCT/GB91/01421 Example lo: P~eparation of ~ '-bis(tetrahydrothio~henium chlo ideL-2-methoxY-5-(2'-ethYlhex~loxYl-~-xYlene Tetrahydrothiophene (6.4 ml, 72 mmol) was added to a suspension of 2,5-bis(chloromethyl)-1 methoxy-4-(2'- -ethylhexyloxy)benzene (4.80 g, ~4.4 mmol) in dry methanol (75 ml), The mixture was then heated to 50C for 22 hours. The solvent was completely removed in vacuo, the residue treated with dry acetone, then filtered under suction and dried to give 4.36 g t53%) of ~ ,~ g-bis(tetrahydro~hiophenium chloride) -2-methoxy-5-(2'-ethylhexyloxy)-~-xylene. lHNMR (250.1 MHz, CD30D) : ~ = 0.89 ~ 1~04 (M), 1.18 (t,J - 7.0 Hz, 3H), 1.29 - 1.65 (m, 8 ~), 1.82 (m, 1 H), 2.32 - 2.55 (m, 8 H), ~.50 -4.56, 4.57 (both s, 2 H, CH2Cl), 7.38 and 7.39 (both s, 1 H, arom. H). IR ~KBr) : 2s4B (broad, m), 1514 (s), 1460 (m), 1399 (s), 1312 (m), 1229 (s), 1033 (s), 703 cm~l (m).
Exam~le 11 A mixture of ~ , ~'-bis(tetrahydrothiophenium chloride)-p-xylene ~0.92 ~, 2.6 mmol) and ~ bi~i(tetrahydrothiophenium chloride)-2-methoxy-5-(2'-ethylhexyloxy~-~-xylene (0.11 g, 0.22 mmol) in methanol (10 ml) was deo~ygenated with argon and cooled with an ice-bath. An argon deoxygenated ice-cold aqueous sodium hydroxide solution (O.4 M, 2.6 mmol, 6.5 ml) was added dropwise and the reaction mixture was le~t to stir for 2.5 hours at 0C under iner~ atmosphere. The re~ction was ~erminated by addition of hydrochloric acid (0.4 M, 0.8 ml). The ~iscous solution was then dialyzed against deoxygenated distilled water (3 x 2000 ml) over 3 days using cellulose membrane dialysis tubing with a molecular weight cut-off of 12,400 (supplied by Sigma Chemical Company Ltd, - 30 Dorset, U.K.). The solven~ was completely removed in vacuo at room tempera~ure from the material remaining in the dialysis tubing. The residue was dissolved in dry methanol (20 ml). IR spectra of copolymers: Fiqure 22.
: . , , ~ -; .. ~: , .
: . .
2~18~8 Example 12 A solution of 1,4-bis(chloromethyl) 2-methoxy-5-(2'-ethylhexyloxy) benzene (0.95 g, 2.9 mmol) and ~
'-dichloro-~-xylene (0.05 g, 0.29 ~mol) in dry tetrahydrofuran (20 ml) was added to a solution of potassium tert-butoxide (95%, 2.5 g, 22 mmol) in dry tetrahydrofuran (120 ml) over 15 min. The mixture was then stirred at room temperature for 21.5 hours. The resulting orange mixture was reduced to 10%
of its volume and poured into met~anol (500 ml). The precipitate was filtered under suction and recrystallised from tetrahydrofuran/methanol to afford 101 mg of polymer. lH
NMR (CD2C12) : Figure 24. IR spectra of copolymers:
The absorption spectra of MEH-PPV, 5% PPV/95% MEH-PPV and 20%
PPV/80% MEH-PPV are shown in Figure 26. The photoluminescent spectra (Figure 27a, 26b, 3la) show that the luminescence is - as expected of higher energy with increasing number of PPV
units. EL devices were made in a standard configuration with IT0 and aluminium contacts and the material showed electroluminescence (Figure 29a, 29b, 30a and 30b). The corresponding electroluminescence spectra are illustrated in Figure 2~a and 28b. Both the 5% PPV/95~ ME~-PPV and the 20%
PPV/80% ~EH-PPV had a turn-on voltage of about 8 V.
Exam~le 13 The previous PPV EL d~vices were constructed with PPV prepared via a Tetrahydrothiophenium (THT)-leaving precursor polymer (Figure 3~a) spun from methanolic solution. This precursor is unstable with respect to its conjugated product and is fully converted by heating at 220C for 2 hours (Figure 32c).
~, .. .. .
~ J2/03491 PCT/GB9l/0142l - 35 - 2~9~
By replacing the THT-leaving group with a metho~y (MeO)-leaving group a more stable precursor (Figure 32b) is formed. This can be easily processed by spin coating from a solution in chloroform (as can the TH~-precursor from methanolic solution). Thermal conversion of the MeO-leavin~
PPV precursor at 300C in vacuo for 12 hours gives very little thermal elimination leaving a copolymer of conjugated and unconjugated units (Figure 32d). This is clearly ssen from the absorption spectra of the THT-leaving PPV and the 10 MeO-leaving PPV (Figure 33). The absorption spectra of the precursors of both are very similar. A significant change occurs in the absorption spectrum of the THT-leaving PPV
(Figure 3~); an insignificant change occurs in the absorption spectrum of the MeO-leaving PPV (Figure 35). Clearly both products are subsequently very stable against subsequent ?
changes at room temperatures and are very suitable as emittin~ -materials in comm~rcial EL devices.
A device was mads with the MeO-leaving PPV. An ITO substrate was cleaned in an ultrasound bath, of first acetone and 20 su~sequently propan-2-ol. The precursor material was then spin-coated on the su~strate. The device was then thermally converted at 300C in vacuo for 12 hours. A top contact of Aluminium was then deposited to define an active area by vacuum deposition at a pressure of less than 6.10 6torr to a thickness of 2-SOOA.
The performance of the device shows no deterioration over those made with PPV prepared via a TH~ leaving group precursor polymer with a turn on voltage below 10V, a diodic current-voltage characteristic and a largely linear ; 30 current-luminance response and a slightly improved quantum , efficiency by at least a factor of ~ (Figures 36 and 37).
,~ ! ' . ' . , ~ .
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WO92/0~91 PCr/GB91/0142 - 36 _ 2 ~ ~L~
The emission spectrum of the ~eO-leaving PPV is markedly different with a peak emission at 2.5eV compared with 2.25eV
in THT-leaving PPV. The emission is a bluey-green as opposed to a greeny-yellow in the case of the THT-leaving PPV. This is again consistent with the MeO-leaving PPY as converted being a copolymer of conjugated and unconjugated sequences:
emission coming from the small conjugated sequences but at a higher energy than in fully conjugated PPV, (Figure 37).
Thus by careful conversion conditions it is possible using copolymers of PPV to obtain electroluminescent emission of different colours and with improved efficiencies.
Example 14 `;
The random copolymers of PPV and DMeOPPV give a means to controlling the bandqap of a conjugated polymer and the potential ~or the construction of multicolour EL devices and channel waveguides.
The copolymers are prepared initially in a precursor form which is soluble in ~ethanol and consists of at least 3 distinct monomer units - a PPV precursor monomer unit with a THT-leaving group, a DMeOPPV monomer unit with a T~T-leaving group and certainly a DMeOPPV monomer unit with a MeO-leavinq group (formed by the methanolic solution substitutionally ; attacking ~he DMeOPPV THT~leaving units) as seen by the strong 1094~ 1 adsorption in the infrared absorption spectra of both the MeO-leaving homopolymer precursor of D~eOPPV and all the copolymer precursor polymers. 'There is possible a small amount of a four~h monomeric unit- a PPV monomer unit with a - MeO-leaving group (formed by the methanolic solution substitutionally attacking the PPV THT-leaving units) ~Figure 30 39(a)).
'' , . ' ` ' ' : .
~ 32/0~91 PCT/GB91/01421 - 37 - 2~9~81 Thin rilms (of the order of l000A as used in EL devices) of the copolymYrs can be obtained by spin-coatinq the precursor solutions. Thermal con~ersion of the said films gives mechanically and thermally robust films. It is found that by linearly varying the copolymer monomer unit ratio that the absorption edge o~ the converted copolymers may ~e accurately controlled (Figure 40). Typically films are con~erted at 220C for 2 hours. ~ore fully conjugated material has a lower bandgap. The controlled increase in bandgap with additional DMeOPPV to PPV units indicates an associated decrease in conjugation. FTIR data shows that the copolymers are only partially conjugated as converted (Figure 4l). There is still a significant absorp~ion at 1094cm 1 indicating monomeric units of DMeOPPV wi~h the methoxy lea~ing group have not been converted to the conjugated form leaving a copolymer of conjugated sequences and unconjugated sequences. The degree of conjugation will thus vary with the number of DMeOPPV Units present (Figure 42).
To convert fully the homopolymer of DMeOPPV with the methoxy leaving group it is necessary to heat the precursor in the presence of acid to catalyse the loss of the methoxy group.
As the THT-leaving group leaves, acid i~; also generated. Thus in the copolymers of PPV and DMeOPPV it is possi~le further to convert the monomeric units of D~eOPPV with the methoxy leaving group to the conjugated fo~m, so lowering the bandgap further and yiving more control of the bandgap, by methods of internally trapping ~he self produced acid where excess acid may damage electrodes or si~ply by heating the precursor films in the presence of acid.
; 30 By converting a spun-coated film of a copoly~er at ~20C in an argon flow which has been passed through concentrated HCl for 2 hrs it is clearly seen that the abso~ption bandgap of the polymer is shifted to lower energy over a similar fllm ;
W092/0~91 PCT/GB91/0142 ~ ~
- 38 - 2~
converted at 220C ln _acuo indicati~ that the "acid"
converted film is more fully conjugated. FTIR absorption measurements support this with the disappearance of the 1094cm 1 absorption only when the copolymer is "acid"
converted. Again it is noted that 2 hours conversion by either technique gives stable material against further change (Figures 43 and 4l).
By converting a spun-coat~d cop~lymer film on a glass substra~e initially with a low temperature bake in vacuo at about lO0 C the diffusion rate of the acid ions out of the film is redu~ed giving an enhanced proba~ility of causing ; conversion of methoxy~leaving units. A subsequent bake at 220C n vacuo yields fully stable material at room temperature again. ~ considerable reduction in bandgap is so obtained over material hea~ed directly to 220C ln vacuo.
Thus there is a further method for controlling the bandgap of these materials (Figure 44).
It should be emphasised that any method of controlling the bandgap in these conjugated polymers equally controls the colour of emitted light in an electroluminescent device (or the colour of photoluminescence under optical excitation) as the wavelength o~ the emitted light largely follows the bandgap o~ the material (an increase in the bandgap of the material causes a similar decrease in the wavelength of the emitted light). The spatial limit for this spatial control of bandgap across the polymer ~il~ is of the order of the thic~ness of the polymer film i.e. lOOOA.
Another film of copolymer (30% Copolymar) was spun-coated onto a glass substrate and ~efore thermal conversion 500A of Aluminium were vacuum deposited at a pressure of less than 6.lO 6 torr via a shadow mask. The sample was then baked ln vacuo for 20 hours at 220C to facilitate full conversion.
The sample ~as then Ptched in weak sodium hydroxide solution ' .
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~ 92/03491 P~/GB91/01421 _ ~9 _ %~ ~:9 ~ ~ ~
to remove the aluminium. The polymer film was unaffected by the etching process. However, the polymer is left patterned.
Where the aluminlum was, the polymer to the eye is a deeper - orange colour indicating a greater degree of conjugation due to enhanced trapping of the acid ions in the polymer film by the aluminium. This is born out by the shift to lower energy of the absorption edge (Figure 45) and the photolumin~scence emission (Figure 46) of th~ dar~ region originally covered by the aluminium. Thus the bandgap o~ the copolymers may again be controlled and moreover in different reqions of the same film giving rise to the possibility of multicolour emission from a single EL device.
Such patterning also has an application in the manufacture of channel waveguides. Another such patterned device as above was made (from 10% copolymer) and there were the same associated lowering of bandgap and absorption edge where tha aluminium had been etched from (Figure 47) and lowering in energy o~ the photoluminescence emission ~rom the same area (Figure 48). The refractive indices of the two regions at ` 20 633nm were measured by coupliny light into the first TE modes from a He-Ne laser. The refrartive index of the less conjugated material was measured to be! 1.564 (0.002) and that of the more conjugated ma~erial (as converted under the encapsulation of aluminium) was measured to be 1.620 (0.002).
This result is in keeping with simple dispersion theory for propagation o~ light in a dielectric ~edium such that the refractive index varies inversely with bandgap. Thus the patte~ning of the polymer allows also ~he spatial control of - refractive index across a polymer film to a length scale of the order of 1000~. For typicaI waveguidin~ structures (such as a channel waveguide) it is necessary to define channels of material to a precision o~ the order but no smaller ~han the wavelength of the light to be guided (i.e~ for the 633nm emission from a He-Ne laser to a precision of the order of ~; 6000A) with a higher refractive index than of the surrounding .; .
, . -~ : ..
',''' " , ' ' WO92/0~91 PCT/GB91/0142 ~ f _ 40 ~ $3 material. Clearly this method of patterning the copolymers ~f PPV and DMeOPPV is amenable to making wavequide structures as high refractive index regions can be defined to a size smaller than the wavelength of light which is to ~e con~ined in the high index region and guided.
In order to characterise more fully the nature o~ the resulting copolymers the absorption spectra were obtained from ; samples which had been spun onto glass under th~ same conditions as discussed below for the construction of devices (step (c)) and subsequently thermally converted side by side with the corresponding devices (step (d)). The results thus provide a direct insight into the effect upon the polymer electronic structure of the copolymer composition. Figure 2a shows a set of spectra for the compositions of the copolymers (of general structure II with R = OCH3) of para-phenylene vinylene, 2,5-dimethoxy-para-phenylene vinylene and unconverted pre~ursor units that have been investigated in device structures and whose per~ormance is exemplified below.
The spectra have all been scaled to the same peak absorption to allow a ready comparison of the onsets for their ~ to~ *
optical transitions and the energies of their absorption peaks. Also shown for comparison is ~e absorption spectrum of the PDMOPV homopolymer obtained as previou~ly shown in "Polyarylene vinylene films prepared from precursor polymers soluble in organic solvents", S. Tokito et al, Polym~r 31, 1137 (l990). There i~ a clear ~rend in these spectra that the energy of the absorption peak shifts to higher energy as the relative content, in ~he precursor copolymer (structure I with R = OCH3 and Rl,~2=-(CH~)4-), of units of the precursor to 2,5-dimethoxy-para-phenylene vinylene is increased. This beha~iour is contrary to expectation for a - fully conjugated copolymer since as discussed above and shown in Figures 2a and 2b, PDMOPV has a lower energy gap than PPV.
In Figure 2a, curve (a) is 100% PPV, (b) is 95% PPV/5~ PDMOPV, (c) is 90~ PPV/l0% PDMOPV, (d) is 85% PPV~l5% PD~OPV, (e) is ~ .
~ 92/0~91 PCT/GB91/01421 - 41 - 2089~8~
ao% PPV/20~ PDMOPV and (f) is 70~ PPV/30% PDMOPV. Similarly this has been observed with 95% PPV/5% MMP~PPV, 90% PPV/lO~
MMP-PPV and 80% PPV/20% MMP-PPV ~Figure l9) and with 95%
PPV/5% MEH-PPV, 90% PPV/lO% MEH-PPV and 80% PPV/20% MEH-PPV
(Figure 23). The data is however consistent with incomplete conversion of the precursor units during the thermal treatment, resulting in remnant non-conjugated sequences that interrupt the -electron delocalisation (structure II with R =
OC~3), limiting the effective conjugation length and thus increasing the ~ to~ * transition energy. These remnant sequences are mostly associated with the precursor to 2,5-dimethoxy-para-phenylene vinylene however, there can also be methoxy leaving groups associated with the precursor to PPV, i.e. the methoxy leaving sroup precursor polymer to PPV, which will not be fully elimi~a ed by thermal treatment (structure II with R = OMe). _~e lac~ of conversion of the methoxy precursors to 2,5-dimethoxy-para-phenylene vinylene and to para-phenylene vinylene under the thermal conversion procedure utilised here is ascribable to the difficulty of elimination of the methoxy lea~ing group, previously shown in "Polyarylenevinylene films prepared from precursor polymers soluble in organic solvents" S. Tokito, T. Momii, H. Murata, T. Tsutsui and S. Saito, Polymer 31, 11.37 ~l990) to require acid catalysis for its full removal. I:t should be e~phasised that while the conversion of the precursors to PPV does in fact liberate acid as one of its by-products, in thin film copolymer samples conYerted by heating in vacuo the acid is - too rapidly removed to be effecti~e in driving the conversion of the precursor to 2,5-dimethoxy-para-phenylene vinylene to completion. In thic~ film samples prepared by static solution casting, howaver, the extent of conversion of the methoxy precursors is significantly enhanced. This is clearly evidencPd in their colour (they are unfortunately too thick for optical absorption measurements3 which, un1ike the uniformly yellow thin film samples, becomes increasingly red as the con~ent of the precursor to 2,5-dimethoxy-para-: . ..
'~ ' , :' ~ ' ,:
- ~2 --phenylene vinyl~ne ln the copolymers increases. It is also evidencPd by the decrease of the strength, during conversion, of the characteristic C-O stretch vibration in the infrared spectra that is associated with the methoxy modifier group on the benzylic carbon of the methoxy precursors to 2,5-dimethoxy-para-phenylene vinylene and para-phenylene vinylene. This behaviour can be understood as being due to the lower ra~e of loss o~ acid from the bulk of thic~ films, allowing greater interaction with the units of the methoxy precursors and consequently a greater extent of their conversion. Fur~her evidence supporting these differences between the thin, spin-coated films and thicker solution cast films comes from their photoluminescence spectra. Discussion nere is limited to the representati~e cases of the copolymers obtained following thermal conversion of thin spin-coated and thick solution cast films of the copolymer precursors prepared from (1) 10% of units of the precursor to 2,5-dimethoxy-para-phenylene vinylene/90% of units of the precursor to para-phenylene vinylene and (2) 20% of units of the precursor to 2,5-dimethoxy-para-phenylene vinylene/80~ of units of the precursor to para-phenylene vinylene. In Figure 3(a) and (b) are shown respectively the emission spectra for thin spin-coated and thic~ solution ca~st films for case (1).
In Figure 4(a) and (b) are shown the correspondinq spectra for case (2). For comparison Figures 5(a) and (b) show the photoluminesc~nce spectra for the PPV and PDMOP~
` homopolymers; the latter prepared via acid catalysed thermal con~rsion under HC1 containing nitrogen gas flow so as to ensure substantial, i~ no~ wholly comple~e, conversion of the precursor units. It is im~ediately clear from the spectra in - Figures 3 and 4 that in vacuo thermally converted spin-coated thin films have siynificantly di~ferent emission spectra ~o the thicker films obtained under identical conversion conditions and from the same precursor solutions but following static solution casting. Furthermore, whils~ the spectra of the thin spin-coated samples have spectra which lie at higher :. . ,. .:. -.:
w~ ,2/n~91 2 ~ 8 9 ~ ~ ~ PCT/GB91/01421 energy than in PPV (Figure 5(a)), the thicker static solutioncast samples show spectra that are red shifted relative to PPV
and hence that are shifting towards the emission spectrum seen in PDMOPV (Figure 5(b)).
It is thus clear that the electronic structures of the copolymers that are incorporated into device structures may be controlled by the sslection of the constituent components present in ~he copolymer precursor and by the conversion conditions used in device fabrication~ Changing some of the units of the precursor to para-phenylene vinylene to units of the precursor to 2,5-dimethoxy-para-phenylene vinylene can have two different effects depending on whether conversion is purely thermal or also invol~es acid catalysis. For purely thermal conversion there is an incomplete elimination such that the resultant conjugated segments are separated by remnant non-conjugated precursor units, causing the energy gap to increase relative to that of homopolymex PPV and the photoluminescence emission to be blue shifted, occuring at :;~ higher energy than in PPV. For acid c,atalysed thermal conversion the elimination is substantially complete with the ; result that the energy gap decreases and photoluminescence emission shifts to the red.
A similar situation arises in the case of the copolymers of the precursor to para-phenylene vinylene and the precursor to 2,5-thienylene vinylene ~structure IT with ~ = H and R' -;.~ C~3) with the absorption spectra of thin spin-coated films of in vacuo thermally converted copolymers showinq a shift in the position of the absorption peak to higher energy than seen in PPV ~see Fisure 6) whilst the photoluminescence emission spectra for thic~ solution cast films converted under identical conditions show a red shift relative to that in PPV
(see Fi~ure 7 (a), (b) and (c)). In Fi~ure 6, curve (a) is 100% PPV, (b) is 95% PPV/5% PTV and (c) is 90% PPV/l0~ PTV.
Thus, the conversion of me~hoxy modifier group precursor units t of 2,5-thienylene vinylene is enhanced in thick films by acid ', 2ID89d~3 1 WO92J0~s1 PCT/GB91/01421~;.
catalysed elimination driven by the acid by-product of the para-phenylene vinylene sulphonium-salt-precursor conversion.
It was previously reported in "Optical Excitations in Poly(2,5-thienylenP vinylene)", A.J. Brassett, N.F. Colaneri, D.D.C. ~radley, R.A. Lawrence, R.H. Friend, H. Murata, S.
Tokito, T. Tsutsui and S. Saito, Phys. Rev. B 41, 10586 (1990) that the photoluminescence emission from the PT~
homo~olymer obtained by acid catalysed thermal conversion of the ~ethoxy leaving group precursor polymer is extremely weak (with ~uantum yield less than or of order l0 5) and, when it can be observed, appears at energies above the onset for to 11 * optical transitions.
In the copolymers of the precursors to para-phenylene vinylene and 2,5-dimethyl-para-phenyl2ne vinylene (structure (I) with R=OCH3 and Rl,R2=-(CH2)4-) the absorption spectra of in vacuo thermally converted thin spin-coated samples show a shift in the position of the absorption peak to higher enerqy than seen in PPY (see Figure 8) whilst the photoluminescence emission spectra for thick solution cast films converted under identical conditions show little shift relative to that in PPV
(see Figure 9(a), (b) and (c)). In Figure 8, curve (a) is 100~ PPV, (b) is 95-~ PPV/5~ DMPPV and (c) is 90~ PPVtlO~
DMPPV. The explanation of the higher bandgap energy obsrved in the absorption spectra of`the thin spin-coated samples is that the as-formed copolymer contains disruption in the conjugation due either to steric interactions of the methyl group with the vinylic proton twisting the sp2- ~ -orbitals of the dimethyl-para-phenylene and the adjacent vinylene units out of planarity or that in the absence of acid catalysed conversion, ~he elimination of methoxy leaving groups from the methoxy precursors to 2,5-dimethyl-para-phenylene vinylene and para-phenylene vinylene is incomplete, thus resulting in a copolymer structure containing conjugated segments separated from each other by unconverted non-conjuqated precursor units or a combination of both.
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W~9V0~91 2 0 8 9 4 8 ~ PCT/GB91/01421 The inventors have trapped some of the acid released fro~ a thin film during thermal conversion by capping a section of a film of the lO~ dimethoxy-PPV/90% PPV precursor polymer which had been spin coated onto a gl~ss slide (about 2~S cm square) with a strip of evaporated aluminium (about 4 mm wide) before heat treatment. The precursor was then heated as described above to leave a film of thickness lOO nm and the aluminium was removed using dilute aqueous sodium hydroxide. There was a clear difference in colour between the area previously coated with aluminium (orange) and that where there had been no aluminium (yellow). The optical absorption spectra for the two areas are shown in Figure 16 from which it can be seen that there is a shift in band gap towards the red of about 0.2 -eV for the area previously coated with aluminium. The photoluminescent spectra for the two regions are shown in Figure 17. This shows that we can control the extent of conjugation in different regions of the same polymer film so as to produce different emission colours from these different regions.
20 Fabrication of Electroluminescent (ELl Structures Structures ~or an EL de~ice require two electrode~ to either side of the emissive region. For the examples shown here, devices have been fabricated by deposition of a series of layers onto a transparent substrate (glass~, but other structures can also be made, with the active (i.e. emissive) area being defined by patterning within the plane of the polymer film~
- The choice of electrode ma~erials is determined by the need to achieve efficient injection o~ charge carriers into the 30 polymer film, and it is desirable to choose materials which pre~erably inject electrons and holes as the ne~ative and positive electrodes respectively. In International Patent Application No. PCT/GB90/OOS84 (Publication No. PCT!W09013148) , , . ~
: . . ~ , :
. ~ . .
WO92/0~91 2 ~ 3 9 ~ ~ ~ PCT/GB91/0142~, is described the use of PPV as the emissive layer, ancl a choice of aluminium, amorphous silicon, silver/magnesium alloy as the negative electrode, and aluminium with a thin oxide coating, gold and indium oxide as the positive electrode.
Many of these combinations were found to be satisfactsry. In the present disrlosure, where many different compositions of copolymers have been investigated, the choice of contact layers has been generally ~or convenience that of aluminium for the negative electrode and alumini~m with an oxide coating as the posi~ive electrode. Calcium has also bee~ used as the negative electrode wi~h indium/tin oxide as the positive electrode. It is to be expected that results obtained with this combination give a good indication of the behaviour to be expected with other choices for electrode materials:
The procedure used for all devices used in this work is as follows:
(a) Clean glass substrates (microscope slides) in propan-2-ol reflux.
(b) Deposit bottom contact of al~inium by evaporation of aluminium in a standard vacuum evaporator (base pressure 2 x 10 6mbar). Four strips lm~ wid~ were usually deposited, and the aluminium film thickness was chosen to give a ~ conducting but semi-transparen~ film (9-12nm). The aluminium ; was then exposed to air at room temperature, to allow for~ation of a surface oxide coating.
(c) Deposition of the precursor polymer from solution in ~ ^
methanol by spin-coating, using a Dyna-Pert PRS14E
spin-coater. This was performed inside a laminar-flow cabinet, with a spin speed of 2000 rev/min, and produced films of polymer in the thic~ness range 50-150nm.
(d) Thermal treatment of the precursor, to convert to the conjugated polymer. This was carried out in an evacuated . . .
, , .
~ 92/0~191 _ 47 _ 2 ~ 8 ~ ~ ~ . PCT/GB91/01421 oven (base pressure lO 5mbar) inside an argon-atmosphere glove box. The heat treatme~t used was 30 min to heat to 220C, between 2 and 5 hours at 220C, and 3 hours to cool to room temperature.
, (e~ Evaporation of aluminium top contact, carried out as in (b) above, but with the lm~ wide strips rotated by 90, to give a total of 16 independently addressable de~ices, each lmm2. The aluminium thickness ~ere was typically 50nm, to ensure a good coverage, and to provide some encapsulation to keep oxygen away from the active parts of the device.
Measurements of ~evices Positive bias wa~ applied to the bottom contact (aluminium with surface oxide coating) using a progra~mable voltage source (Keithley model 230). The current through the device was measured with a Xeithley model 195 DVM connected between the top contact and ground. The light output was measured with a large area silicon photovoltaic cell (lcm2 active area, Radio Spares catalogue number RS 303-674).
Typical results of the PPV homopolymerl, a copolymer obtained : 20 by in vacuo thermal convQrsion o~ spin~coating thin films of spin coated films of a precursor copol~mer synthesised from 90~ para-phenylene vinylene/lOS 2,5-dimethoxy-para-phenylene ~ vinylene precursor units, a copolymer obtained by in vacuo -~ thermal conversion of spin-coat~d thin films of a precursor -~ copolymer synthesised fro~ ~0% para-phenylenQ vinylene/lo%
2,5~thienylene vinylene precursor units and a copolymer obtained by in vacuo thermal conversion o~ spin-coated thin ~il~s of a precursor copolymer synthesised from 90%
para-phe~ylene vinylene/10% 2-methoxy-5-(2'-methylpentyloxy) -para-phenylene vinylene precursor units are shown in Figures 10, 11, 12, 20 and 21 which present the current versus voltage and light ou~put versus current charac~eristics. In Figure lO
. -WO92/0~91 PCT/CB91/01421~-- ~8 - 2~
the bottom contact thickness is ll0A, the top contact thic~ness is 1300A and the thickness of the electroluminescent layer is 900A. In Figure ll the corresponding thickness values are 120A, l000A and l~SOA and in Figure 13 they are 90A, 1370A and 1070A. Similar current versus voltage characteristics were found for all devices, with a threshold voltage for current injection of around 25 to 40V. There was also found a broadly linear relation between current and light output (which allows ~he efficiency of the device to be characterised simply, by the gradient of this plot).
It is found that the light output varies strongly with the choice of copolymer, and that some of the copolymers show very s~rongly enhanced efficiencies as measured against the - ef~iciency of the PPV homopolymer. The variation of the quantum efficiency is shown as actually measured (current in photodetector/current through EL device) in Fic3ures 13, 14, 15 and 31 for the copolymers obtained from the n vacuo thermal conversion of spin-coated thin films of precursor copolymers formed between the precursors to PPV ancl PDMOPV, the precursors to PPV and PTV, the precursors to PPV and PD~PV, and the precursors to PPV and MMP-PPV respectively. The plots ` show some data for a large number of devices, and there is some scatter evident between devices of the same nominal composition. This may be due to inhomoc~eneities in the devices, such as non-unifo~m thickness, entrapped dust particlas etc. and it is considered that the ~etter values of efficiency at each compo~ition give a true indication of the intrinsic behaviour o~ the EL structure. The PPV/PDMOPV
copolymers show a very big improvement in efficiency for PDMOPV in the range 5-15~, with best results at lO~, for which the improvement over that obtained for PPV is by a ~actor of about 50. The PPV/PTV copolymers do not show such behaviour.
This may be compared with the very low quant~m yield for photoluminescence (less than or of order l0 5) that is found in the homopolymer, as in "Optical Excitations in . . , -: ' ' ;' ' :
~ 2/0~91 _ 49 _ 2 0 8 ~ ~ 8 1 PCT/GB91/01421 Poly(2,5-thienylene . ~/lene)", A.J. Brassett, N.F. Colaneri, D.D.C. Bradley, R.A. Lawrence, R.H. Friend, H. Murata, S. Tokito, T. Tsutsui and S. Saito, Phys. Rev. B
41, 10586 (l990). For the PPV/PDMPV copolymers an improvement over the PPV homopolymer is seen at 10% PDMPV, but the changes are less marked than with the PPV/PDMOPV
~he maximum measured e~iciencies for the devices shown here, obtained for the 90/10% PPV/PDMOPV copolymer, approach %. To obtain the real efficiency of the EL layer in the device it is necessary to correct for the efficiency of the photodetector (50~), the collection efficiency for the EL
~24%) and the optical transmittance of the Al semitransparent layer (30%). Wi~h these factors included, it is estimated that ~he real efficiency of the EL layex in such a device is as high as O. 3% . This value compares very favourably with the performance of EL devices fabricated with other materials.
As PL and EL are due to the same excited state in the polymer, . as evidenced by the similarity in emis~;ion recorded for a : 20 single polymer film, a correspondence between ef~iciency for EL and for PL is broadly to be expected. However, there are some differences as discussed below.
~ The efficiency for luminescence is in part an intrinsic .~ property of the material (that is to say that it has the same - value for all samples), and possibly also dependent on the actual form of the sample and the nature of the interaces to it. Thus, it might ~e expected for the thin films used for the ~L structures that migration of the excited states to the interfaca between the polymer film and the electrode material --migh~ result in non-radiative decay of ~he excited state, and - thus allow the efficiency for luminescenca to fall below its "intrinsic" value. The effect, then of restricting the motion :: of the excited states in the copolymers may be to improve quantum yield both by improving the intrinsic properties of :. .
, , W09t/0~91 ~$~ $~ PCT/GB91/01421~.
the polymer, and also by reducing the motion of excited states to the interface region. Thus, the improvements in quantum yield that have been measured in EL for some o~ the copolymers are by a very large factor (x 50), considerably larger than the factor ~y which the yield for PL is improved.
There has been described a design technique and a method of manufacture for achieving especially efficiant emission in conjugated copolymer electrol~minescent structures through the use of the local modulation of semiconductor energy gap, between the highest occupied and lowest unoccupied energy levels, achieved in copolymers of two or more different monomer units. The modulation of energy gap is achieved by the use, in the copolymer structure, of chemically-dif~erent mono~r units which in their individual homopolymer forms have dif~erent energy gaps. The effect of the energy gap modulation is to produce local regions that are potential energy minima and that act to confine the exciton states created by injection of electrons and holes from the contact layers. This confinement is ~eneficial for efficient radiative recom~ination of excitons through its reduction of the opportunities ~or migration o~ the excitons to non-radiative recombination sites subsequent to their initial ; generation and thus leads to a higher electroluminescent yield.
The copolymers described herein are intractable, insGluble in ~ommon solvents and infusible at temperatures below the ~`~
decomposition temperature, or they are soluble in a ~ew organic solvents.
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