Organic field effect transistor with a photostructured gate dielectric, method for the production and use thereof in organic electronics

Information

  • Patent Grant
  • 7238961
  • Patent Number
    7,238,961
  • Date Filed
    Tuesday, January 29, 2002
    23 years ago
  • Date Issued
    Tuesday, July 3, 2007
    17 years ago
Abstract
The invention relates to an organic field effect transistor which is especially characterized by a cross-linked, structured insulating layer (4) on which the gate electrode (5) is arranged. The structure of the OFET ensures that the gate electrode (5) of an OFET can be used as a strip conductor to the source electrode (2) of the next transistor and can be used in the construction of larger circuits.
Description
CROSS REFERENCE TO RELATED APPLICATIONS

This is the 35 USC 371 national stage of international application PCT/DE02/00312 filed on Jan. 29, 2002, which designated the United States of America


FIELD OF THE INVENTION

The present invention relates to organic field effect transistors, so-called OFETs, with photopatterned gate dielectric as well as a method for the production thereof, and the use of said field effect transistors in organic electronics.


BACKGROUND OF THE INVENTION

Field effect transistors play a central role in all areas of electronics. In order to adapt them to suit particular applications, it has been necessary to make them lighter and more flexible. The development of semiconducting and conducting polymers has made it possible to produce organic field effect transistors, all parts of which, including the semiconductor layer as well as the source, drain and gate electrodes, are fabricated from polymeric materials.


However, in the production of organic field effect transistors a plurality of organic layers have to be patterned one on top of the other in order to obtain an OFET of normal construction, as shown in FIG. 1. This is possible only to a very limited extent using conventional photolithography which is actually used for patterning inorganic materials. The operations normally involved in photolithography dissolve or attack the organic layers and therefore make them unusable. This occurs, for example, when a photoresist is spun on, developed and stripped off.


This problem has been solved using an organic field effect transistor as described in Applied Physics Letters 1998, page 108 et seq. A polyaniline-coated polyimide film is used as the substrate. In this first polyaniline layer, the source and drain electrode are formed by irradiation through a first mask. In this first layer, a semiconductor layer of polythienylenevinylene (PTV) is also formed, on which polyvinylphenol is then crosslinked using hexamethoxymethylmelamine HMMM. This layer is used as the gate dielectric and as an insulator for the next layer and the interconnects. A further polyaniline layer is finally formed thereon in which the second layer of interconnects and the gate electrode is defined by patterning. The vertical interconnects are produced mechanically by punching pins through the layers.


The above method prevents previously applied layers from being dissolved or otherwise damaged. However, it has been shown that in particular the last operation for forming the vertical interconnects (otherwise known as vias) does not permit the fabrication of complex circuits.


Applied Physics Letters 2000, page 1487 describes how this problem can be solved by providing low-resistance vias in the field effect transistor structure by means of photopatterning of photoresist material. To this end, another design of OFET, namely a so-called “bottom gate” structure, is regarded as indispensable. If a “top gate” structure of the same composition were produced, this would result in unacceptable contact resistances in the order of Mcustom character.


However, the construction and the operations for patterning this OFET with bottom gate structure are complex, making it impossible to manufacture particularly complex circuits economically.


SUMMARY OF THE INVENTION

The object of the present invention was therefore to specify an organic field effect transistor or a method for the manufacture thereof which permits the use of photolithography without attacking or dissolving the organic layers in all operations as well as making possible a construction which provides a simple means of vertical interconnection between conducting tracks at different levels in organic integrated circuits. The organic field effect transistors must at the same time be manufacturable cheaply and economically using simple operations.


The subject matter of the present invention is therefore an organic field effect transistor characterized in that, on a flexible substrate there are disposed, in a first layer, source and drain electrodes as well as a semiconductor on which, in a second layer, an insulator is pattern-formed and onto which, in a third layer, a gate electrode is deposited (top gate structure).


The organic field effect transistor according to the invention is light and extremely flexible, as it is only formed from organic layers which are mainly patterned by means of photolithography but without using photoresist. By means of the patterning of the insulator layer in particular, the gate electrode of the organic field effect transistor according to the invention can simultaneously be used as the conducting track to the source electrode of the next transistor.


Advantageous embodiments of the subject matter of the invention will emerge from the sub-claims 1 to 10.


Thus ultrathin glasses, but for cost reasons preferably plastic foils, can be used as the substrate. Polyethylene terephthalate and polyimide foils are particularly preferred. The substrate must in each case be as light and flexible as possible. As the thickness of the substrate determines the actual thickness of the device as a whole—all the other layers combined are only some 1000 nm thick—the substrate thickness must also be kept as small as possible, normally in the range of approximately 0.05 to 0.5 mm.


The source and drain electrodes can consist of wide variety of materials. The type of material will basically be determined by the type of fabrication preferred. Thus, for example, electrodes of indium tin oxide (ITO) can be produced by photolithography on ITO-coated substrates, the ITO being etched away from the areas not covered by photoresist. Polyaniline (PANI) electrodes can also be produced either by photopatterning or by photolithography on PANI-coated substrates. Equally, electrodes made of conductive polymers can be produced by printing the conductive polymer directly onto the substrate. Conductive polymers include, for example, doped polyethylene (PEDOT) or possibly PANI.


The semiconductor layer consists, for example, of conjugated polymers such as polythiophenes, polythienylenevinylenes or polyfluorene derivatives which are solution processable by spin-coating, silk-screening or printing. Also suitable for creating the semiconductor layer are so-called “small molecules”, i.e. oligomeres such as sexithiophene or pentacene, which are evaporated onto the substrate by a vacuum technique.


However, an important aspect of the present subject matter of the invention is the way in which the insulator layer is created. This is a crosslinked insulator which is crosslinked and patterned by means of photolithography, i.e. under partial exposure. An insulator material is crosslinked area by area using a crosslinker under acid catalysis. Suitable insulator materials in the context of the present invention include poly(4-hydroxystyrene) or melamine-formaldehyde resins containing hydroxyl groups. The crosslinker is acid-sensitive, specifically hexamethoxymethylmelamine (HMMM). Acid catalysis is effected by means of a photoinitiator, e.g. diphenyliodonium tetrafluoroborate or triphenylsulfonium hexafluoroantimonate which produce an acid under the effect of light.


The present invention relates to a method for producing an organic field effect transistor wherein a flexible substrate is provided with a source and drain electrode as well as a semiconductor and is characterized in that an insulator is deposited on the semiconductor by applying an insulator material solution containing an acid-sensitive crosslinker as well as a photoinitiator, exposing it through a shadow mask covering the source and drain electrodes, and then baking it, crosslinking being effected at the exposed areas and the gate electrode being deposited on the thus crosslinked and patterned insulator.





BRIEF DESCRIPTION OF THE DRAWING

Details and preferred embodiments of the method according to the invention will emerge from the sub-claims 12 to 18. The invention will now be described in further detail with reference to FIGS. 1 to 3 and an exemplary embodiment.


In the accompanying drawings:



FIG. 1 shows the construction of a conventional OFET;



FIG. 2 shows the construction of an OFET according to the invention; and



FIG. 3 shows chemical reactions underlying the production of the crosslinked, patterned insulator layer.





DETAILED DESCRIPTION OF THE INVENTION

A conventional OFET consists of a substrate 1, source and drain electrodes 2 and 2′, a semiconductor 3, an insulator 4 and the gate electrode 5. The conventional OFET requires contact tags 6 for combining individual OFETs to form larger circuits.


As shown in FIG. 2, the starting point for producing an OFET according to the invention is a similar structure to that of a conventional OFET. In other words, on a substrate 1 there are formed source and drain electrodes 2 and 2′ as well as a semiconductor layer 3. The source and drain electrodes 2 and 2′ as well as the semiconductor 3 are in one layer. On this layer a thin layer of an insulator material such as poly(4-hydroxystyrene) (PVP) or melamine-formaldehyde resins containing hydroxyl groups is deposited by spin-coating, screen printing or similar processes. The solution to be applied contains, in addition to the insulator material, an acid-sensitive crosslinker such as hexamethoxymethylmelamine (HMMM) and a photoinitiator such as diphenyliodonium tetrafluoroborate or triphenylsulfonium hexafluoroantimonate. This layer 4a is then exposed through a shadow mask 7, preferably with UV light. As a result of exposure, the photoinitiator produces an acid in accordance with reaction scheme (a) in FIG. 3 which effects the crosslinking between the insulator material and the crosslinker under the effect of temperature, i.e. in a subsequent baking operation (reaction scheme (b) in FIG. 3). Baking is performed at relatively low temperatures, approximately between 100° C. and 140° C., preferably at 120° C. This ensures that the unexposed areas remain uncrosslinked, as higher temperatures are required for crosslinking in the absence of a catalyst. In a final development step, the uncrosslinked insulator is removed by rinsing with a suitable solvent, such as n-butanol or dioxan. As shown in FIG. 2, a crosslinked and patterned insulator layer 4b on which the gate electrode is finally applied as described above is thereby produced directly on top of the semiconductor layer 3.


With the present method, the gate dielectric is therefore produced by photolithography without using photoresist. This results in an OFET whose gate electrode can be used simultaneously as the conducting track to the source electrode of the next transistor. This allows vertical interconnection between conducting tracks at different levels in organic integrated circuits.


An exemplary embodiment of this will now be disclosed, specifically indicating the reaction conditions.


EXEMPLARY EMBODIMENT FOR PRODUCING A GATE DIELECTRIC

5 ml of a 10% solution of poly(4-hydroxystene) in dioxan are mixed with 20 mg hexamethoxymethylmelamine and a catalytic trace of diphenyliodonium tetrafluoroborate and spin-coated onto a substrate already containing electrodes and semiconductor. The substrate is exposed through a shadow mask and then baked for 30 minutes at 120° C. After cooling, the insulator is removed at the unexposed and therefore uncrosslinked areas by intensive rinsing with or soaking in n-butanol. The gate electrode is formed thereon.


The OFETs according to the invention are ideally suitable for applications in the field of organic electronics and in particular for the production of identification stickers (ID tags), electronic watermarks, electronic barcodes, electronic toys, electronic tickets, for use in product or piracy protection or anti-theft security.

Claims
  • 1. Organic field effect transistor, comprising: a flexible substrate;a first layer on the substrate;source and drain electrodes and a semiconductor in the first layer;an insulator forming a second layer on the first layer, the insulator being pattern-formed and formed from an insulator material crosslinked with a crosslinker in the presence of a photoinitiator, the insulator pattern being produced by crosslinking the insulator in the desired pattern by photolithography with uncrosslinked insulator outside the pattern and then removing the uncrosslinked insulator material; anda gate electrode on the second layer forming a third layer.
  • 2. Organic field effect transistor according to claim 1, wherein the substrate is an ultrathin glass foil or a plastic foil.
  • 3. Organic field effect transistor according to claim 2, wherein the substrate is polyethylene terephthalate or a polyimide foil.
  • 4. Organic field effect transistor according to claim 1, wherein the source and drain electrodes are formed from indium tin oxide (ITO), polyaniline (PANI) and/or conductive polymers.
  • 5. Organic field effect transistor according to one of claim 1, wherein the semiconductor is formed from conjugated polymers or oligomers.
  • 6. Organic field effect transistor according to claim 1, wherein the insulator material is selected from poly(4-hydroxystyrene) or from melamine-formaldehyde resins containing hydroxyl groups.
  • 7. Organic field effect transistor according to claim 1, wherein the crosslinker is acid-sensitive, including hexamethoxymethylmelamine (HMMM).
  • 8. Organic field effect transistor according to claim 1, wherein the photoinitiator is selected from diphenyliodonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
  • 9. Organic field effect transistor according to claim 1, wherein the gate electrode is formed from polyaniline, other conductive polymers or carbon black.
  • 10. Use of the organic field effect transistor according to claim 1 in organic electronics.
  • 11. Use of the organic field effect transistor according to claim 1 for identification stickers (ID tags), electronic watermarks, electronic barcodes, electronic toys, electronic tickets, in product or piracy protection or anti-theft security.
  • 12. Organic field effect transistor according to claim 1, wherein the insulator pattern is produced by patterning the insulator with photolithography without using a photoresist.
  • 13. Method far producing an organic field effect transistor comprising: providing a flexible substrate with a source and drain electrode and a semiconductor;forming an insulator from an insulator material crosslinked with a crosslinker in the presence of a photoinitiator by applying an insulator material solution containing an acid-sensitive crosslinker and a photoinitiator to the semiconductor;exposing the insulator through a shadow mask covering the source and drain electrodes;patterning the insulator pattern by crosslinking the insulator in the desired pattern by photolithography with uncrosslinked insulator outside the pattern and then removing the uncrosslinked insulator material including baking to effect the crosslinking and patterning of the insulator at the exposed areas; anddepositing a gate electrode on the thus crosslinked and patterned insulator.
  • 14. Method according to claim 13, wherein the insulator material is selected from poly(4-hydroxystyrene) or melamine-formaldehyde resins containing hydroxyl groups.
  • 15. Method according to claim 13, wherein the crosslinker is acid-sensitive, including hexamethoxymethylmelamine (HMMM).
  • 16. Method according to claim 15, wherein the photoinitiator produces an acid under the effect of light and is selected specifically from diphenyliodonium tetrafluoroborate and triphenylsulfonium hexafluoroantimonate.
  • 17. Method according to claim 13, wherein the solution containing the insulator material, the crosslinker and the photoinitiator is applied by spin-coating or silk screen printing.
  • 18. Method according to claim 13, wherein UV light used for exposure.
  • 19. Method according to claim 13, wherein baking is performed at a temperature between 100° C. and 140° C.
  • 20. Method according to claim 19, wherein baking is performed at a temperature of 12° C.
Priority Claims (1)
Number Date Country Kind
101 05 914 Feb 2001 DE national
PCT Information
Filing Document Filing Date Country Kind 371c Date
PCT/DE02/00312 1/29/2002 WO 00 8/11/2003
Publishing Document Publishing Date Country Kind
WO02/065557 8/22/2002 WO A
US Referenced Citations (93)
Number Name Date Kind
3512052 Maclver et al. May 1970 A
3769096 Ashkin Oct 1973 A
3955098 Kawamoto May 1976 A
4246298 Guarnery et al. Jan 1981 A
4302648 Sado et al. Nov 1981 A
4340657 Rowe Jul 1982 A
4442019 Marks Apr 1984 A
4554229 Small, Jr. Nov 1985 A
4865197 Craig Sep 1989 A
4926052 Hatayama May 1990 A
4937119 Nikles et al. Jun 1990 A
5173835 Cornett et al. Dec 1992 A
5206525 Yamamoto et al. Apr 1993 A
5259926 Kuwabara et al. Nov 1993 A
5321240 Takahira Jun 1994 A
5347144 Garnier et al. Sep 1994 A
5364735 Akamatsu et al. Nov 1994 A
5395504 Hoffman et al. Mar 1995 A
5480839 Ezawa et al. Jan 1996 A
5486851 Gehner et al. Jan 1996 A
5502396 Desarzens Mar 1996 A
5546889 Wakita et al. Aug 1996 A
5569879 Gloton et al. Oct 1996 A
5574291 Dodabalapur et al. Nov 1996 A
5578513 Maegawa Nov 1996 A
5580794 Allen Dec 1996 A
5625199 Baumbach et al. Apr 1997 A
5630986 Miller May 1997 A
5652645 Jain Jul 1997 A
5691089 Smayling Nov 1997 A
5705826 Aratani et al. Jan 1998 A
5729428 Sakata et al. Mar 1998 A
5854139 Kondo et al. Dec 1998 A
5869972 Birch et al. Feb 1999 A
5883397 Isoda et al. Mar 1999 A
5892244 Tanaka et al. Apr 1999 A
5967048 Fromson et al. Oct 1999 A
5970318 Choi et al. Oct 1999 A
5973598 Beigel Oct 1999 A
5994773 Hirakawa Nov 1999 A
5997817 Crismore et al. Dec 1999 A
5998805 Shi et al. Dec 1999 A
6036919 Thym et al. Mar 2000 A
6045977 Chandross et al. Apr 2000 A
6072716 Jacobsen et al. Jun 2000 A
6083104 Fung Jul 2000 A
6087196 Sturm et al. Jul 2000 A
6133835 De Leeuw et al. Oct 2000 A
6150668 Bao et al. Nov 2000 A
6180956 Chondroudis et al. Jan 2001 B1
6197663 Chandross et al. Mar 2001 B1
6207472 Calligari et al. Mar 2001 B1
6215130 Dodabalapur Apr 2001 B1
6221553 Wolk et al. Apr 2001 B1
6251513 Hyatt et al. Jun 2001 B1
6284562 Batlogg et al. Sep 2001 B1
6300141 Segal et al. Oct 2001 B1
6321571 Themont et al. Nov 2001 B1
6322736 Bao et al. Nov 2001 B1
6329226 Jones et al. Dec 2001 B1
6330464 Colvin et al. Dec 2001 B1
6335539 Dimitrakopoulos et al. Jan 2002 B1
6340822 Brown et al. Jan 2002 B1
6344662 Dimitrakopoulos et al. Feb 2002 B1
6362509 Hart Mar 2002 B1
6384804 Dodabalapur et al. May 2002 B1
6403396 Gudesen et al. Jun 2002 B1
6429450 DeLeeuw et al. Aug 2002 B1
6498114 Amundson et al. Dec 2002 B1
6517995 Jacobson et al. Feb 2003 B1
6555840 Hudson et al. Apr 2003 B1
6593690 McCormick et al. Jul 2003 B1
6603139 Tessler et al. Aug 2003 B1
6621098 Jackson et al. Sep 2003 B1
6852583 Bernds et al. Feb 2005 B2
20020002284 Heeger et al. Jan 2002 A1
20020018911 Bernius et al. Feb 2002 A1
20020022284 Heeger et al. Feb 2002 A1
20020025391 Angelopoulos et al. Feb 2002 A1
20020053320 Duthaler May 2002 A1
20020056839 Joo et al. May 2002 A1
20020068392 Lee et al. Jun 2002 A1
20020130042 Stiene Sep 2002 A1
20020170897 Hall Nov 2002 A1
20020195644 Dodabalapur et al. Dec 2002 A1
20030059987 Henning et al. Mar 2003 A1
20030112576 Brewer et al. Jun 2003 A1
20030175427 Loo et al. Sep 2003 A1
20040002176 Xu Jan 2004 A1
20040013982 Jacobson et al. Jan 2004 A1
20040026689 Bernds et al. Feb 2004 A1
20040084670 Tripsas et al. May 2004 A1
20040211329 Funhata et al. Oct 2004 A1
Foreign Referenced Citations (146)
Number Date Country
33 38 597 May 1985 DE
4243832 Jun 1994 DE
198 52312 May 1999 DE
198 16 860 Nov 1999 DE
19918193 Nov 1999 DE
198 51703 May 2000 DE
100 06 257 Sep 2000 DE
199 21024 Nov 2000 DE
19933757 Jan 2001 DE
69519782 Jan 2001 DE
199 35 527 Feb 2001 DE
199 37 262 Mar 2001 DE
100 12204 Sep 2001 DE
10033112 Jan 2002 DE
100 45 192 Apr 2002 DE
100 47 171 Apr 2002 DE
100 43204 Apr 2002 DE
100 58 559 May 2002 DE
10061297 Jun 2002 DE
101 17 663 Oct 2002 DE
101 20 687 Oct 2002 DE
102 19905 Dec 2003 DE
0 108650 May 1984 EP
0 128 529 Dec 1984 EP
0 268 370 May 1988 EP
0 268 370 May 1988 EP
0 350 179 Jan 1990 EP
0 418504 Mar 1991 EP
0 442123 Aug 1991 EP
0460242 Dec 1991 EP
0501456 Sep 1992 EP
0501456 Sep 1992 EP
0 511807 Nov 1992 EP
0 528662 Feb 1993 EP
0685985 Dec 1995 EP
0716458 Jun 1996 EP
0 785 578 Jul 1997 EP
0 785 578 Jul 1997 EP
0 786820 Jul 1997 EP
0 615 256 Sep 1998 EP
0962984 Dec 1999 EP
0966182 Dec 1999 EP
0 979715 Feb 2000 EP
0981165 Feb 2000 EP
0981165 Feb 2000 EP
0989614 Mar 2000 EP
1 048 912 Nov 2000 EP
1 052 594 Nov 2000 EP
1065725 Jan 2001 EP
1065725 Jan 2001 EP
1 083 775 Mar 2001 EP
1 102 335 May 2001 EP
1 104 035 May 2001 EP
1 103916 May 2001 EP
1 134 694 Sep 2001 EP
1224999 Jul 2002 EP
1237207 Sep 2002 EP
1 318 084 Jun 2003 EP
2793089 Nov 2000 FR
723598 Feb 1955 GB
2 058 462 Apr 1981 GB
54069392 Jun 1979 JP
61167854 Jul 1986 JP
362065477 Mar 1987 JP
05152560 Jun 1993 JP
05259434 Oct 1993 JP
05347422 Dec 1993 JP
08197788 Aug 1996 JP
09083040 Mar 1997 JP
09320760 Dec 1997 JP
09320760 Dec 1997 JP
10026934 Jan 1998 JP
2969184 Nov 1999 JP
2001085272 Mar 2001 JP
WO 93 16491 Aug 1993 WO
WO 9417556 Aug 1994 WO
WO 9506240 Mar 1995 WO
WO 9531831 Nov 1995 WO
WO 95 31831 Nov 1995 WO
WO 96 02924 Feb 1996 WO
WO 9619792 Jun 1996 WO
WO 9712349 Apr 1997 WO
WO 9718944 May 1997 WO
WO 9718944 May 1997 WO
WO 98 18186 Apr 1998 WO
WO 9818156 Apr 1998 WO
WO 9840930 Sep 1998 WO
WO 9907189 Feb 1999 WO
WO 9910929 Mar 1999 WO
WO 99 10939 Mar 1999 WO
WO 99 21233 Apr 1999 WO
WO 99 30432 Jun 1999 WO
WO 99 39373 Aug 1999 WO
WO 99 40631 Aug 1999 WO
WO 9953371 Oct 1999 WO
WO 99 54936 Oct 1999 WO
WO 9954936 Oct 1999 WO
WO 9966540 Dec 1999 WO
WO 0033063 Jun 2000 WO
WO 0036666 Jun 2000 WO
WO 0103126 Jan 2001 WO
WO 0106442 Jan 2001 WO
WO 01 08241 Feb 2001 WO
WO 01 15233 Mar 2001 WO
WO 0115233 Mar 2001 WO
WO 0117029 Mar 2001 WO
WO 0117041 Mar 2001 WO
WO 0127998 Apr 2001 WO
WO 0146987 Jun 2001 WO
WO 01 47044 Jun 2001 WO
WO 01 47045 Jun 2001 WO
WO 0173109 Oct 2001 WO
WO 0173109 Oct 2001 WO
WO 0205360 Jan 2002 WO
WO 0205361 Jan 2002 WO
WO 0215264 Feb 2002 WO
WO 02 19443 Mar 2002 WO
WO 0219443 Mar 2002 WO
WO 0229912 Apr 2002 WO
WO 0243071 May 2002 WO
WO 0247183 Jun 2002 WO
WO 0247183 Jun 2002 WO
WO 02065557 Aug 2002 WO
WO02065557 Aug 2002 WO
WO 02071139 Sep 2002 WO
WO 02071505 Sep 2002 WO
WO 02076924 Oct 2002 WO
WO 02091495 Nov 2002 WO
WO 02 095805 Nov 2002 WO
WO 02095805 Nov 2002 WO
WO 02099908 Dec 2002 WO
WO 0299907 Dec 2002 WO
WO 03046922 Jun 2003 WO
WO 03069552 Aug 2003 WO
WO 03067680 Aug 2003 WO
WO 03081671 Oct 2003 WO
WO 03095175 Nov 2003 WO
WO 2004032257 Apr 2004 WO
WO 2004042837 May 2004 WO
WO2004042837 May 2004 WO
WO 2004047144 Jun 2004 WO
WO 2004047144 Jun 2004 WO
WO 2004047194 Jun 2004 WO
WO 2004047194 Jun 2004 WO
WO 2004083859 Sep 2004 WO
WO 00 79617 Dec 2004 WO
Related Publications (1)
Number Date Country
20040219460 A1 Nov 2004 US