EP1523698A1 - Polymerizable composition, polymer, resist, and lithography methods - Google Patents

Polymerizable composition, polymer, resist, and lithography methods

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Publication number
EP1523698A1
EP1523698A1 EP03787737A EP03787737A EP1523698A1 EP 1523698 A1 EP1523698 A1 EP 1523698A1 EP 03787737 A EP03787737 A EP 03787737A EP 03787737 A EP03787737 A EP 03787737A EP 1523698 A1 EP1523698 A1 EP 1523698A1
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EP
European Patent Office
Prior art keywords
resist
polymerizable composition
proportion
radicals
writing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03787737A
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German (de)
French (fr)
Inventor
Klaus Elian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Infineon Technologies AG
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Infineon Technologies AG
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Publication date
Application filed by Infineon Technologies AG filed Critical Infineon Technologies AG
Publication of EP1523698A1 publication Critical patent/EP1523698A1/en
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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F30/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F30/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F30/08—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains

Definitions

  • the invention relates to a polymerizable composition according to the preamble of claim 1, a polymer according to claim 6, a resist according to claim 7 and a lithography method according to the preamble of claim 11.
  • Photomasks such as those used in semiconductor lithography, currently mostly consist of a transparent quartz glass plate to which a structured, non-transparent chrome layer is applied (COG: Chrome on Glass). So-called mask blanks are used in the manufacturing process; These are quartz glass plates, which are covered with a continuous / chrome layer that is currently approx. 30 to 100 nm thick.
  • COG Chrome on Glass
  • These mask blanks are coated with a light or electron sensitive photoresist (resist) and e.g. using a laser or electron beam recorder to describe it in a targeted manner with any layout.
  • the photoresist layer is then developed and, in the case of the positive resist, the photoresist is removed at the points described above. In the case of a negative resist, however, the varnish is removed from the unexposed areas.
  • the result is a relief-like image of the previously written structure in the photoresist;
  • the photoresist now protects the chrome layer at defined points (depending on the resist system, the previously exposed or unexposed), whereas the chrome is exposed between these points and can be further processed in a targeted manner.
  • the further treatment in mask production is a targeted removal of the chrome layer by plasma etching.
  • the structure previously created in the resist is transferred into the chromium layer by removing the exposed (not protected by resist) chromium in a reactive ion plasma consisting, for example, of a chlorine / oxygen gas mixture.
  • Chromium-halogen oxides are transferred in order to be effectively removed in the end.
  • this high oxygen content attacks the photoresist on the chrome very strongly, so that it is also gradually removed, particularly laterally.
  • Resist lines are e.g. "Shrinked" by values of approximately 30 to 60 nm per edge. This reduced geometry is also transferred to the chrome layer, so that after the etching process, the authenticity of the chrome structures (compared to the theoretical
  • Layout structure is not guaranteed. As a frequently occurring rule of thumb, approximately 50 nm loss (overetching) currently occurs per structure edge; which means that structure lines are generally approx. 100 nm narrower after etching than the theoretical layout.
  • OPC Optical Proximity Correction Features
  • the present invention has for its object to provide a resist and an electron writing method with which the etching loss can be reduced.
  • a resist with the features of claim 1.
  • the subject matter of claim 1 is a monomer of a resist which solves the problem of chromium etching loss through a significantly increased etching stability compared to the chlorine / oxygen plasmas used in mask production.
  • the invention solves the problem by using a special monomer with which resist with a greatly increased stability compared to the etching plasmas used is used.
  • the proposed photoresist contains chemically bound silicon. Surprisingly, this results in a significantly increased etching stability in the final chrome etching process compared to all other commercial lacquers.
  • the silicon is oxidized in the highly oxygen-containing etching plasma to form non-volatile silicon dioxide, which greatly limits or prevents the lateral resist shrinkage.
  • the resist and chromium etching loss is limited to almost zero, which means that no structural reserve has to be written in the electron beam writing process.
  • the requirements for the mask writing resolution are reduced to such an extent that the future technology generations of the 70 and 50 nm masks can be mastered with the mask writing devices. Without the reduction of the chrome etching loss, the future devices would not be able to cope with these technology deaths due to the still existing resolution limitation.
  • Ri, R 2 , R 3 H or alkyl radicals (preferably H or methyl radicals)
  • R 4 , R 5 alkyl radicals (preferably methyl radicals), or further silicon units, for example siloxane units
  • R 6 alkyl radical (preferably tert-butyl radical)
  • R 7 H or alkyl radical (preferably methyl radical)
  • These monomers can be, for example, by radical polymerization with themselves or together with others
  • Monomers e.g. maleic anhydride, styrene, p-hydroxystyrene, methacrylic acid or the like
  • Monomers are simply polymerized and thus used as the basic component in resists according to the invention.
  • the silicon content in the polymer By increasing the silicon content in the polymer, the dimensional stability of the lacquer layer is improved. It can be expected that the silicon content is between 5-25% by weight depending on the monomer used.
  • a typical resist mix can e.g. consist of:
  • solvent methoxypropyl acetate, ethyl acetate, ethyl lactate, cyclohexanone, gamma-butyrolactone, methyl ethyl ketone, etc.
  • the resist can be used in a laser or electron beam lithography process.
  • photo acid generator e.g. Crivello salts, triphenyl sulfonium sulfonates, diphenyl iodonium sulfonates, phthalimidosulfonates, ortho-nitrobenzyl sulfonates, or the like
  • the resist can be used in a laser or electron beam lithography process.
  • a mask blank is coated with the resist solution according to the invention. Then the resist is written with a laser and / or
  • Electron beam recorder A heating step can, but does not have to be carried out subsequently.
  • the resist described is then washed with an aqueous alkaline developer medium (e.g. 2.38% aqueous tetraethylammonium hydroxide solution,
  • Standard TMAH developer e.g. using a reactive ion plasma (RIE) to dry-etch the mask blank with a chlorine / oxygen gas mixture.
  • RIE reactive ion plasma
  • the ethereal phase is separated off via a separating funnel and dried over calcium chloride for 24 hours. It is filtered off and the filtrate is added dropwise to an ice-cooled solution of 50 mmol of di-butyl pyrocarbonate in anhydrous diethyl ether within 1 h. The reaction mixture is shaken thoroughly 3 times with water, then the organic phase is separated off in a separating funnel and again dried over calcium chloride for 24 hours. Rotating off the diethyl ester gave the product with strong impurities as a yellowish liquid.
  • This polymer can be used as a base component for mixing resist.
  • the embodiment of the invention is not limited to the preferred exemplary embodiments specified above. Rather, a number of variants are conceivable which make use of the polymerizable composition according to the invention, the polymer, the resist and the lithographic process even in the case of fundamentally different types.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a polymerizable composition for producing a resist, containing at least one unsaturated polymerizable monomer (I, II) with at least one silicon atom and at least one carbonyl group. The invention also relates to a resist produced by polymerizing these compositions and to lithography methods.

Description

Beschreibungdescription
Polymerisierbare Zusammensetzung, Polymer, Resist und Lithographieverfahren .Polymerizable composition, polymer, resist and lithography process.
Die Erfindung betrifft eine polymerisierbare Zusammensetzung nach dem Oberbegriff des Anspruchs 1, ein Polymer nach Anspruch 6, einen Resist nach Anspruch 7 und ein Lithographieverfahren nach dem Oberbegriff des Anspruchs 11.The invention relates to a polymerizable composition according to the preamble of claim 1, a polymer according to claim 6, a resist according to claim 7 and a lithography method according to the preamble of claim 11.
Fotomasken, wie sie in der Halbleiterlithographie eingesetzt werden bestehen derzeit zumeist aus einer transparenten Quarzglasplatte, auf die eine strukturierte, nicht transparente Chromschicht aufgebracht ist (COG: Chrome on Glas) . Im Herstellungsprozess verwendet man dazu sogenannte Maskenblanks; das sind Quarzglasplatten, die flächig mit einer derzeit ca. 30 bis 100 nm dicken durchgehenden / Chromschicht bedeckt sind.Photomasks, such as those used in semiconductor lithography, currently mostly consist of a transparent quartz glass plate to which a structured, non-transparent chrome layer is applied (COG: Chrome on Glass). So-called mask blanks are used in the manufacturing process; These are quartz glass plates, which are covered with a continuous / chrome layer that is currently approx. 30 to 100 nm thick.
Diese Maskenblanks werden mit einem licht- bzw. elektronenempfindlichen Fotolack (Resist) belackt und z.B. mittels Laser- oder Elektronenstrahlschreiber ganz gezielt mit einem beliebigen Layout beschrieben. Anschließend wird die Fotolackschicht entwickelt und der Fotolack im Falle des Positivresists an den vorher beschriebenen Stellen entfernt. Im Falle eines Negativresists wird der Lack dagegen an den unbelichteten Stellen entfernt.These mask blanks are coated with a light or electron sensitive photoresist (resist) and e.g. using a laser or electron beam recorder to describe it in a targeted manner with any layout. The photoresist layer is then developed and, in the case of the positive resist, the photoresist is removed at the points described above. In the case of a negative resist, however, the varnish is removed from the unexposed areas.
Es resultiert ein reliefartiges Abbild der vorher geschriebenen Struktur im Fotolack; der Fotolack schützt die Chromschicht nun an definierten Stellen (je nach Resistsystem die vorher belichteten oder unbelichteten) , wogegen das Chrom zwischen diesen Stellen freiliegt und gezielt weiterbehandelt werden kann.The result is a relief-like image of the previously written structure in the photoresist; The photoresist now protects the chrome layer at defined points (depending on the resist system, the previously exposed or unexposed), whereas the chrome is exposed between these points and can be further processed in a targeted manner.
Die Weiterbehandlung ist in der Maskenherstellung eine gezielte Entfernung der Chromschicht durch Plasmaätzung. Die zuvor im Resist erzeugte Struktur wird hierbei in die Chromschicht übertragen, indem das freiliegende (nicht durch Resist geschützte) Chrom in einem reaktiven Ionenplasma, bestehend z.B. aus einer Chlor/Sauerstoff-Gasmischung, entfernt wird.The further treatment in mask production is a targeted removal of the chrome layer by plasma etching. The The structure previously created in the resist is transferred into the chromium layer by removing the exposed (not protected by resist) chromium in a reactive ion plasma consisting, for example, of a chlorine / oxygen gas mixture.
Das Problem hierbei ist allerdings, dass für eine ausreichende Entfernbarkeit des Chroms in die Gasphase mit hohen Sauerstoffanteilen im Plasma gearbeitet werden muss. Das Chrom muss dabei in leicht flüchtige Chromoxide bzw.The problem with this, however, is that high chromium contents in the plasma must be used to ensure sufficient chromium removal. The chromium must be converted into volatile chromium oxides or
Chrom-Halogenoxide überführt werden, um letztendlich effektiv entfernt werden zu können. Dieser hohe Sauerstoffanteil greift allerdings den auf dem Chrom befindlichen Fotolack sehr stark an, so dass dieser auch insbesondere lateral sukzessive entfernt wird. Auf dem Chrom befindlicheChromium-halogen oxides are transferred in order to be effectively removed in the end. However, this high oxygen content attacks the photoresist on the chrome very strongly, so that it is also gradually removed, particularly laterally. On the chrome
Rresistlinien werden während des Ätzens z.B. pro Kante um Werte von ca. 30 bis 60 nm „geschrumpft". Diese verkleinerte Geometrie wird auch auf die Chromschicht übertragen, so dass nach dem Ätzprozess die Originalgetreuheit der Chromstrukturen (im Vergleich zur theoretischenResist lines are e.g. "Shrinked" by values of approximately 30 to 60 nm per edge. This reduced geometry is also transferred to the chrome layer, so that after the etching process, the authenticity of the chrome structures (compared to the theoretical
Layoutstruktur) nicht gewährleistet ist. Als häufig auftretende Daumenregel treten pro Strukturkante derzeit ca. 50 nm Verlust (Uberätzung) auf; was gleichbedeutend ist, dass Strukturlinien grundsätzlich nach Ätzen ca. 100 nm schmäler sind als laut theoretischem Layout vorgesehen.Layout structure) is not guaranteed. As a frequently occurring rule of thumb, approximately 50 nm loss (overetching) currently occurs per structure edge; which means that structure lines are generally approx. 100 nm narrower after etching than the theoretical layout.
Bei den bisher geforderten Zielstrukturgrößen (Strukturdimensionen größer gleich 0,25μm) konnte dieser Ätzverlust u.U. noch toleriert werden, da der Verlust an der Maßhaltigkeit bereits im Design durch ein verändertesIn the case of the target structure sizes previously required (structure dimensions greater than or equal to 0.25 μm), this etch loss could possibly can still be tolerated, as the loss of dimensional accuracy is already changed in the design due to a change
Schreiberlayout korrigiert wurde, indem bereits bei der Strukturierung der Fotolackschicht zu erzeugende Gräben lOOnm schmäler bzw. zu erzeugende Linien lOOnm breiter geschrieben wurden. Durch diesen Schreibvorhalt konnte der Ätzverlust bereits im Vorfeld ausgeglichen werden. Nicht mehr tolerabel ist dieser Schreibvorhalt allerdings bei der Herstellung von Masken mit Strukturdimensionen von weniger 0,25/xm, insbesondere ab der Technologie-Generation für 70nm Strukturen.Corrected the layout of the recorder by writing trenches lOOnm narrower or structuring lines lOOnm wider already when structuring the photoresist layer. This write retention enabled the loss of etching to be compensated for in advance. However, this writing requirement is no longer tolerable in the production of masks with structure dimensions of less than 0.25 / xm, in particular from the technology generation for 70nm structures.
Zwar arbeitet man hier immer noch nach dem Prinzip der 4x Reduktion, d.h. die Strukturen auf der Maske dürfen noch vier Mal so groß sein, als sie später auf dem Wafer abgebildet werden, aber insbesondere die nichtabzubildenden optischen Hilfsstrukturen auf der Maske (Optical Proximity Correction features (OPC) ) erreichen hier bereits eine Größendimension, die mit den dann verfügbaren Maskenscheiben (Laser- oder Elektronenschreibverfahren) nicht mehr realisiert werden kann. Die OPC-Zusatzstrukturen haben z.b. bereits in sehr naher Zukunft Dimensionen von lOOnm und weniger und müssen in definiertem Abstand von den HauptStrukturen auf der Maske sein. Bei diesen feinen Strukturdimensionen ist eine Vorabkorrektur des Layouts (Strukturvorhalt) nicht mehr möglich, da z.B. bei einem Sollabstand von 100 nm und gleichzeitigem Soll -Strukturvorhalt von jeweils 50 nm pro Kante die Strukturen schon im Layout zu einer einzigen zusammenfallen würden. Selbst wenn dies bei einem unkritischeren Abstand von z.B. 150 nm noch nicht der Fall sein sollte, würde derzeit aber kein Resist den bleibenden Abstand von 50nm, auflösen.You still work according to the principle of 4x reduction, i.e. The structures on the mask may still be four times as large as they will later be imaged on the wafer, but in particular the optical auxiliary structures not to be imaged on the mask (Optical Proximity Correction Features (OPC)) already reach a size dimension here, which then corresponds to that available mask disks (laser or electron writing process) can no longer be realized. The additional OPC structures have e.g. dimensions of lOOnm and less in the very near future and must be on the mask at a defined distance from the main structures. With these fine structure dimensions, it is no longer possible to correct the layout beforehand (structure retention), e.g. with a nominal distance of 100 nm and a simultaneous nominal structure reserve of 50 nm per edge, the structures would already collapse into a single layout. Even if this is at a less critical distance of e.g. 150 nm should not yet be the case, but currently no resist would resolve the remaining distance of 50 nm.
Einzige Möglichkeit zur Lösung dieses Problems: Der Ätzverlust muss drastisch reduziert werden (Target-Wert: Ätzverlust = Null) .The only way to solve this problem: The etching loss must be drastically reduced (target value: etching loss = zero).
Der vorliegenden Erfindung liegt die Aufgabe zugrunde, einen Resist und ein Elektronenschreibverfahren zu schaffen, mit dem der Ätzverlust reduziert werden kann..The present invention has for its object to provide a resist and an electron writing method with which the etching loss can be reduced.
Diese Aufgabe wird erfindungsgemäß durch einen Resist mit den Merkmalen des Anspruchs 1 gelöst. Gegenstand des Anspruchs 1 ist ein Monomer eines Resists, welches das Problem des Chrom-Ätzverlustes durch eine deutlich erhöhte Ätzstabilität gegenüber den in der Maskenherstellung verwendeten Chlor/Sauerstoff-Plasmen löst.This object is achieved according to the invention by a resist with the features of claim 1. The subject matter of claim 1 is a monomer of a resist which solves the problem of chromium etching loss through a significantly increased etching stability compared to the chlorine / oxygen plasmas used in mask production.
Die Erfindung löst das Problem, indem ein spezielles Monomer verwendetet wird, mit dem Resist mit stark erhöhter Stabilität gegenüber den eingesetzten Ätzplasmen eingesetzt wird. Gegenüber allen bisher beim Maskenschreiben üblicherweise eingesetzten Lacksystemen enthält der vorgeschlagene Fotolack chemisch eingebundenes Silizium. Daraus resultiert überraschenderweise gegenüber allen anderen kommerziellen Lacken eine deutlich erhöhte Ätzstabilität im abschließenden Chromätzprozess. Das Silizium wird im stark sauerstoffhaltigen Ätzplasma aufoxidiert zu nichtflüchtigem Siliziumdioxid, was den lateralen Resistschwund sehr stark einschränkt bzw. verhindert.The invention solves the problem by using a special monomer with which resist with a greatly increased stability compared to the etching plasmas used is used. Compared to all the coating systems previously used in mask writing, the proposed photoresist contains chemically bound silicon. Surprisingly, this results in a significantly increased etching stability in the final chrome etching process compared to all other commercial lacquers. The silicon is oxidized in the highly oxygen-containing etching plasma to form non-volatile silicon dioxide, which greatly limits or prevents the lateral resist shrinkage.
Durch die sehr stark erhöhte Ätzstabilität wird der Resist- und Chromätzverlust auf nahezu Null eingeschränkt, was bedeutet, dass im Elektronestrahl-Schreibprozess kein Strukturvorhalt mehr geschreieben werden muss. Dadurch sind die Anforderungen an das Maskenschreiberauflösungsvermögen soweit reduziert, dass mit den Maskenschreibern die zukünftigen Technologiegenerationen der 70 und 50 nm Masken bewältigt werden können. Ohne die Reduzierung des Chromätzverlustes würden auch die zukünftigen Geräte aufgrund der immer noch vorhandenen Auflösungsbegrenzung diese Technologienodes überhaupt nicht bewältigen können.Due to the greatly increased etching stability, the resist and chromium etching loss is limited to almost zero, which means that no structural reserve has to be written in the electron beam writing process. As a result, the requirements for the mask writing resolution are reduced to such an extent that the future technology generations of the 70 and 50 nm masks can be mastered with the mask writing devices. Without the reduction of the chrome etching loss, the future devices would not be able to cope with these technology deaths due to the still existing resolution limitation.
Die Verwendung des vorgeschlagenen Fotolackes erfordert für die Produktion keinen zusätzlichen Aufwand oder Geräte; es findet exakt die gleiche Prozessierung statt wie bereits bei den seit einigen Jahren eingesetzten bisherigen Fotolacksystemen. Im folgenden werden zwei vorteilhafte Monomere beschrieben, mit denen ein erfindungsgemäßer Resist herstellbar ist. Die erste Ausführungsform ist in Fig. 1, die zweite in Fig. 2 dargestellt. Dabei werden folgende Reste verwendet.The use of the proposed photoresist requires no additional effort or equipment for the production; exactly the same processing takes place as with the previous photoresist systems that have been used for some years. Two advantageous monomers are described below with which a resist according to the invention can be produced. The first embodiment is shown in Fig. 1, the second in Fig. 2. The following residues are used.
Ri, R2, R3 : H oder Alkylresste (vorzugsweise H oder Methylreste)Ri, R 2 , R 3 : H or alkyl radicals (preferably H or methyl radicals)
R4, R5 : Alkylreste (vorzugsweise Methylreste), oder weitere Siliziumeinheiten, z.B. SiloxaneinheitenR 4 , R 5 : alkyl radicals (preferably methyl radicals), or further silicon units, for example siloxane units
R6 : Alkylrest (vorzugsweise tert-Butylrestrest) R7 : H oder Alkylrest (vorzugsweise Methylrest)R 6 : alkyl radical (preferably tert-butyl radical) R 7 : H or alkyl radical (preferably methyl radical)
Diese Monomere können zum Beispiel durch radikalische Polymerisation mit sich selbst oder zusammen mit anderenThese monomers can be, for example, by radical polymerization with themselves or together with others
Monomeren (z.B. Maleinsäureanhydrid, Styrol , p-Hydroxystyrol , Methacrylsäure o.a.) einfach polymerisiert werden und somit als Grundkomponente in erfindungsgemäßen Resists eingesetzt werden.Monomers (e.g. maleic anhydride, styrene, p-hydroxystyrene, methacrylic acid or the like) are simply polymerized and thus used as the basic component in resists according to the invention.
Durch die Erhöhung des Siliziumanteils im Polymer wird die Verbesserung der Masshaltigkeit der Lackschicht erreicht. Es kann damit gerechnet werden, dass der Siliziumanteil zwischen 5-25 Gew-% in Abhängigkeit vom verwendeten Monomer liegt.By increasing the silicon content in the polymer, the dimensional stability of the lacquer layer is improved. It can be expected that the silicon content is between 5-25% by weight depending on the monomer used.
Eine typische Resistmischung kann z.B. bestehen aus:A typical resist mix can e.g. consist of:
70-98% Lösungsmittel (Methoxypropylacetat , Ethylacetat, Ethyllactat, Cyclohexanon, gamma-Butyrolacton, Methylethylketon, o.a.)70-98% solvent (methoxypropyl acetate, ethyl acetate, ethyl lactate, cyclohexanone, gamma-butyrolactone, methyl ethyl ketone, etc.)
2-30% polymerisierbare Polymere,2-30% polymerizable polymers,
0,1-10% Photosäurebildner (z.B. Crivello-Salze, Triphenylsulfoniumsulfonate, Diphenyliodoniumsulfonate, Phthalimidosulfonate, ortho-Nitrobenzylsulfonate, o.a.) Erfindungsgemäß ist der Resist in einem Laser- oder Elektronenstrahllithographieverfahren verwendbar .0.1-10% photo acid generator (e.g. Crivello salts, triphenyl sulfonium sulfonates, diphenyl iodonium sulfonates, phthalimidosulfonates, ortho-nitrobenzyl sulfonates, or the like) According to the invention, the resist can be used in a laser or electron beam lithography process.
Dabei wird zunächst ein Maskenblank mit der erfindungsgemäßen Resistlösung belackt. Anschließend erfolgt das Beschreiben des Resists mit einem Laser- und / oderFirst, a mask blank is coated with the resist solution according to the invention. Then the resist is written with a laser and / or
Elektronenstrahlschreiber . Nachfolgend kann, muss aber nicht ein Heizschritt durchgeführt werden. Der beschriebene Resist wird dann mit einem wässrig alkalischen Entwicklermedium (z.B. 2,38%ige wässrige Tetra ethylammoniumhydroxidlösung,Electron beam recorder. A heating step can, but does not have to be carried out subsequently. The resist described is then washed with an aqueous alkaline developer medium (e.g. 2.38% aqueous tetraethylammonium hydroxide solution,
Standard TMAH-Entwickler) entwickelt. Abschließend wird z.B. mit einem reaktiven Ionenplasma (RIE) der Maskenblank mit einer Chlor/Sauerstoff-Gasmischung trockengeätzt. Dabei wird die Chromschicht geätzt; der Fotolack bleibt dabei weitgehend unangegriffen. Damit wird die gleiche Struktur in das Chrom übertragen, die ursprünglich in den Resist geschrieben wurde.Standard TMAH developer). Finally, e.g. using a reactive ion plasma (RIE) to dry-etch the mask blank with a chlorine / oxygen gas mixture. The chrome layer is etched; the photoresist remains largely unaffected. This transfers the same structure to the chrome that was originally written in the resist.
Ausführungsbeispiel der ErfindungEmbodiment of the invention
Im folgenden wird ein Ausführungsbeispiel unter Verwendung des Monomers gemäß Fig. 1 beschrieben.An embodiment using the monomer shown in FIG. 1 will be described below.
50 mmol Allyl-Dimethyl-Chlorsilan werden in 250 ml Diethylether gelöst und unter starkem Rühren im Verlauf von lh mit 250 ml Wasser versetzt und anschließend lh unter Rückfluss zum Sieden erhitzt.50 mmol of allyl-dimethyl-chlorosilane are dissolved in 250 ml of diethyl ether and, with vigorous stirring, 250 ml of water are added over the course of 1 h and the mixture is then heated to boiling under reflux.
Über einen Scheidetrichter wird die etherische Phase abgetrennt und 24h über Calciumchlorid getrocknet . Es wird abfiltriert und das Filtrat innerhalb von lh in eine eisgekühlte Lösung aus 50 mmol Pyrokohlensäuredietrbutylester in wasserfreiem Diethylether getropft. Die Reaktionsmischung wird 3 Mal gründlich mit Wasser ausgeschüttelt, anschließend in einem Scheidetrichter die organische Phase abgetrennt und wiederum 24h über Calciumchlorid getrocknet. Abrotieren des Diethylesters ergab das Produkt mit starken Verunreinigungen als gelbliche Flüssigkeit. Löst man diese Flüssigkeit in 100 ml Methylethylketon, erhitzt zum Sieden und tropft dann innerhalb 2 h eine Mischung aus 50mmol Maleinsäureanhydrid, 5mmol Azoisobutyronitril und 100 ml Methylethylketon dazu, so polymerisiert die Mischung und ergibt nach Abkühlung und Eintropfen in 2 1 Wasser ein fast farbloses Polymer, welches abfiltriert und im Vakuumtrockenschrank bei 50 °C getrocknet wird.The ethereal phase is separated off via a separating funnel and dried over calcium chloride for 24 hours. It is filtered off and the filtrate is added dropwise to an ice-cooled solution of 50 mmol of di-butyl pyrocarbonate in anhydrous diethyl ether within 1 h. The reaction mixture is shaken thoroughly 3 times with water, then the organic phase is separated off in a separating funnel and again dried over calcium chloride for 24 hours. Rotating off the diethyl ester gave the product with strong impurities as a yellowish liquid. If this liquid is dissolved in 100 ml of methyl ethyl ketone, heated to boiling and then a mixture of 50 mmole of maleic anhydride, 5 mmole of azoisobutyronitrile and 100 ml of methyl ethyl ketone is added dropwise within 2 hours, the mixture polymerizes and, after cooling and dropping in 2 l of water, gives an almost colorless polymer , which is filtered off and dried in a vacuum drying cabinet at 50 ° C.
Dieses Polymer kann als Basiskomponente zur Abmischung von Resist verwendet werden.This polymer can be used as a base component for mixing resist.
Die Erfindung beschränkt sich in ihrer Ausführung nicht auf die vorstehend angegebenen bevorzugten Ausführungsbeispiele. Vielmehr ist eine Anzahl von Varianten denkbar, die von der erfindungsgemäßen polymerisierbaren Zusammensetzung, dem Polymer, dem Resist und dem Lithographiverfahren auch bei grundsätzlich anders gearteten Ausführungen Gebrauch machen. The embodiment of the invention is not limited to the preferred exemplary embodiments specified above. Rather, a number of variants are conceivable which make use of the polymerizable composition according to the invention, the polymer, the resist and the lithographic process even in the case of fundamentally different types.

Claims

Patentansprüche claims
1. Polymerisierbare Zusammensetzung zur Herstellung eines Resists, enthaltend mindestens ein ungesättigtes, polymerisierbares Monomer mit mindestens einem Siliziumatom und mindestens einer Carbonylgruppe .1. Polymerizable composition for producing a resist, containing at least one unsaturated, polymerizable monomer with at least one silicon atom and at least one carbonyl group.
2. Polymerisierbare Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, dass ein Monomer durch folgende allgemeine Formel (I) gekennzeichnet ist:2. Polymerizable composition according to claim 1, characterized in that a monomer is characterized by the following general formula (I):
R4 Si R5 R 4 Si R 5
worin bedeuten: in which mean:
Ri, R2/ R3 : H oder Alklyreste, insbesondere Methylreste R4, R5 : Alkylreste, insbesondere Methlyreste, weitereR 1, R 2 / R 3 : H or alkyl radicals, in particular methyl radicals R 4 , R 5 : alkyl radicals, in particular methyl radicals, further
Siliziumeinheiten, z.B. Siloxane R6 : Alkylrest, insbesondere tert-ButylrestSilicon units, for example siloxanes R 6 : alkyl radical, in particular tert-butyl radical
wobei RlΛ R2/ R3, R4 , R5, Rβ gleich oder verschieden sein können .where R lΛ R 2 / R 3 , R 4 , R 5 , Rβ may be the same or different can .
3. Polymerisierbare Zusammensetzung nach Anspruch 1 oder 2, dadurch gekennzeichnet , dass ein Monomer durch folgende allgemeine Formel (II) gekennzeichnet ist :3. Polymerizable composition according to claim 1 or 2, characterized in that a monomer is characterized by the following general formula (II):
worin bedeuten:in which mean:
Ri, R2, R3 : H oder Alklyreste, insbesondere MethylresteRi, R 2 , R 3 : H or alkyl radicals, especially methyl radicals
R , R5 : Alkylreste, insbesondere Methlyreste, Siliziumeinheiten, z.B. Siloxane R Rss : Alkylrest, insbesondere tert-ButylrestR, R 5 : alkyl radicals, in particular methyl radicals, silicon units, for example siloxanes RR ss : alkyl radical, in particular tert-butyl radical
R7 : H oder Alklyrest, insbesondere Methlyrest,R 7 : H or alkyl radical, in particular methyl radical,
wobei Ri, R2, R3, R , R5, R6, R7 gleich oder verschieden sein können .where Ri, R 2 , R 3 , R, R 5 , R 6 , R7 may be the same or different.
4. Polymerisierbare Zusammensetzung nach mindestens einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass mindestens ein Alkylrest eine Kettenlänge von Ci bis C8 aufweist .4. Polymerizable composition according to at least one of the preceding claims, characterized in that that at least one alkyl radical has a chain length of Ci to C 8 .
5. Polymerisierbare Zusammensetzung nach mindestens einem der vorhergehenden Ansprüche , dadurch gekennzeichnet, das zur Polymerisierung Monomere nach Anspruch 1 und / oder andere Monomere, insbesondere Maleinsäureanhydrid, Styrol , p-Hydroxystyrol , Methacrylsäure enthalten sind.5. Polymerizable composition according to at least one of the preceding claims, characterized in that the monomers for polymerizing according to claim 1 and / or other monomers, in particular maleic anhydride, styrene, p-hydroxystyrene, methacrylic acid are included.
6. Polymer hergestellt durch Polymerisation einer der Zusammensetzungen nach Anspruch 1 bis 5.6. Polymer produced by polymerizing one of the compositions according to claims 1 to 5.
7. Resist gekennzeichnet durch einen Anteil zwischen 2 und 30% an Polymer nach Anspruch 6, einem Anteil Lösungsmittel zwischen 70 und 98 % und einem Anteil Fotosäurebildner von 0,1 bis 10 %.7. Resist characterized by a proportion between 2 and 30% of polymer according to claim 6, a proportion of solvent between 70 and 98% and a proportion of photo acid generator from 0.1 to 10%.
8. Resist nach Anspruch 7, gekennzeichnet durch einen Anteil an Methoxypropylacetat , Ethylacetat, Ethyllactat, Cyclohexanon, gamma-Butyrolacton und / oder Methlyethylketon als Lösungsmittel .8. Resist according to claim 7, characterized by a proportion of methoxypropylacetate, ethyl acetate, ethyl lactate, cyclohexanone, gamma-butyrolactone and / or methyl ethyl ketone as solvent.
9. Resist nach Anspruch 7 oder 8, gekennzeichnet durch einen Anteil an Crivello-Salz , Triphenlysulfoniumsulfonat , Diphenyliodoniumsulfonat , Phthalimidosulfonat und / oder ortho-Nitrobenzylsulfonat als Fotosäurebildner.9. Resist according to claim 7 or 8, characterized by a proportion of Crivello salt, triphenlysulfonium sulfonate, diphenyliodonium sulfonate, phthalimidosulfonate and / or ortho-nitrobenzyl sulfonate as photo acid generator.
10. Resist nach mindestens einem der Ansprüche 7 bis 9 zur Verwendung in einem Elektronenstrahlschreibverfahren.10. Resist according to at least one of claims 7 to 9 for use in an electron beam writing method.
11. Lithographieverfahren zur Herstellung einer Struktur auf einem Substrat, insbesondere einer Struktur für eine Lithographiemaske für die Herstellung von Halbleiterbauelementen, dadurch gekennzeichnet, dass ein Resist nach einem der Ansprüche 7 bis 9 verwendet wird. 11. Lithography method for producing a structure on a substrate, in particular a structure for a lithography mask for the production of semiconductor components, characterized in that a resist according to one of claims 7 to 9 is used.
12. Lithographieverfahren nach Anspruch 10, dadurch gekennzeichnet , dass12. Lithography method according to claim 10, characterized in that
a) ein Maskenblank mit einem Resist nach Anspruch 9 belackt wird,a) a mask blank is coated with a resist according to claim 9,
b) Beschreiben des Resists mit einem Laser- und / oder ElektronenstrahlSchreiber,b) writing the resist with a laser and / or electron beam writer,
c) Entwicklung der durch das Beschreiben erzeugten Struktur im Resist,c) development of the structure produced by the writing in the resist,
d) Trockenätzen des Maskenblanks.d) dry etching of the mask blank.
13. Lithographieverfahren nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass nach dem Beschreiben des Resists ein Heizschritt durchgeführt wird.13. Lithography method according to claim 10 or 11, characterized in that a heating step is carried out after writing on the resist.
14. Lithographieverfahren nach mindestens einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, dass die Entwicklung mit einem wäßrigen alkalischen Entwickler, insbesondere einer 2,38-%igen wäßrigen Tetramethlyammoniumhydroxidlsöung oder einem TMAH-Entwickler erfolgt. 14. Lithography method according to at least one of claims 10 to 12, characterized in that the development is carried out with an aqueous alkaline developer, in particular a 2.38% strength aqueous tetramethylammonium hydroxide solution or a TMAH developer.
EP03787737A 2002-07-22 2003-07-21 Polymerizable composition, polymer, resist, and lithography methods Withdrawn EP1523698A1 (en)

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