EP0000702A1 - Process for forming a flow-resistant resist mask of radioation-sensitive material - Google Patents
Process for forming a flow-resistant resist mask of radioation-sensitive material Download PDFInfo
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- EP0000702A1 EP0000702A1 EP7878100337A EP78100337A EP0000702A1 EP 0000702 A1 EP0000702 A1 EP 0000702A1 EP 7878100337 A EP7878100337 A EP 7878100337A EP 78100337 A EP78100337 A EP 78100337A EP 0000702 A1 EP0000702 A1 EP 0000702A1
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- resist
- resist mask
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- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
Definitions
- resist masks in the manufacture of integrated circuits using radiation-sensitive layers containing various organic polymers is known.
- Layers of a radiation sensitive material are applied to a support, exposed to light or other activating radiation such as electron beams or X-rays in an imagewise pattern and developed into a visible image by removing the more soluble portions of the layer in a developer solution.
- the resist pattern is post-cured in the usual way at an elevated temperature.
- the thermoplastic polymer materials in the resist flow at temperatures above their glass transition temperature.
- the object of the invention is a method for producing a flow-resistant resist mask by curing, in which no special device is required for the curing process and in which the resist composition does not have to be modified before exposure.
- the object of the invention is achieved by a method of the type mentioned at the outset, which is characterized in that a curing agent of the o-quinonediazide type is applied to a resist mask, the coated mask is heated and then excess curing agent is removed therefrom.
- the curing agents for use in the process according to the invention are water-soluble salts of o-quinonediazide sulfonic and carboxylic acids.
- Compounds of this type include o-quinonediazides of the benzene, naphthalene and phenanthrene pure. Examples of the compounds have the formulas given below: in which R is SO 3 X or COOX and X is, for example, Na + , K + , Ca 2+ , Ba 2+ , Li + or NH 4 + .
- the concentrations should be kept in a range of about 0.5 to 1.5% by weight to prevent crater formation therein Areas to avoid.
- the solvent system or the hardening agent is water-based, so that attack of the resist layer by the coating solution is avoided. It has been found that the resist layer is better wetted by the coating solution and consequently a more uniform coating of the hardening agent is obtained when a mixture of water with alcohols with 2 to 4 carbon atoms, for example with ethanol, propanol or butanol, is used. The proportions of water and alcohol are chosen so that sufficient solubility of the hardening agent is obtained and at the same time an attack by the solvent on the resist system is avoided.
- surfactants can be added in amounts of about 0.01 to 1% by weight to improve the wetting. Examples of useful surfactants are sodium lauryl sulfate, fluorine surfactants hydrocarbon base, sodium palmitate and polymethacrylic acid solutions.
- the curing agent is applied to the resist mask by conventional methods, for example by dipping, spraying or spinning, to obtain a continuous layer over the resist mask and the base.
- a layer thickness of about 40 nm (400 ⁇ ) is required as a minimum in order to obtain a continuous coating on the surface and the side walls of the resist image.
- a layer thickness of about 50 to 100 nm (500 to 1000 ⁇ ) is preferred.
- the desired layer thickness can be obtained in the spinning technique by varying the spinning speed.
- the S pinnzeit is chosen so that a major part of the solvent is removed by evaporation.
- the resist compositions which can be cured by the process according to the invention can be either positive or negative resist materials.
- Negative resist materials are those that, when irradiated, crosslink and become less soluble.
- Examples of negative resist materials are sensitized polyvinyl cinnamate polymer compositions described, for example, in U.S. Patent 2,732,301 and sensitized, partially cyclized poly-cisisoprene polymer compositions described, for example, in U.S. Patent 2,852,379.
- Examples of positive resist materials which degrade under the action of radiation and thereby become more soluble are sensitized novolak resin compositions which are described, for example, in US Pat. Nos. 3,046,118, 3,046,121, 3,201,239 and 3,666,743.
- the resist layers are applied to a base and exposed imagewise. Then the more soluble areas of the layer, which are the exposed areas in the case of a positive resist and the unexposed areas in the case of a negative resist, are removed with a developer solution.
- the resulting resist mask pattern can then be treated in the process of the invention by covering it with a layer of an o-quinonediazide curing agent. After coating, the resist mask is heated to a temperature which is sufficient to bring about a reaction of the o-quinonediazide with the resist layer, with the formation of a crosslinked outer layer, in particular on the side walls of the resist image, so that the lateral flow of the image is prevented, when the image is heated to temperatures above the glass transition temperatures of the polymer portion of the resist layer.
- the residue of the curing agent which remains on the base at the edges of the resist mask can be easily removed by rinsing with water.
- the resulting resist mask shows little lateral flow of the images.
- the hardened resist image retains its dimensions during subsequent treatments of the exposed areas of the base, for example when hot etching Acids or with a reactive gas plasma, during ion implantation or a metal vapor deposition process, in which the resist layer is heated to higher temperatures.
- a mask pattern of a positive photoresist was formed on the surface of a cleaned, metal-coated silicon semiconductor wafer.
- the resist composition consisted of a phenol formaldehyde novolak resin and the 2-diazo-1-oxo-naphthalene-5-sulfonic acid ester of dihydroxybenzophenone.
- the resist was applied to the metal surface by spinning at 4000 rpm, cured to a dry film thickness of about 2.2 pm for 20 minutes at about 85 ° C. and then imagewise exposed to actinic radiation and developed with an aqueous alkaline developer solution to remove the to remove exposed areas.
- a 1% by weight solution of the sodium salt of 2-diazo-1-oxide-naphthalene-5-sulfonic acid in a mixture of water and isopropanol in a volume ratio of 50 was applied to the resist mask and the wafer by spinning at 3000 revolutions per minute within one minute : 50 plotted.
- the coating thickness was about 50 nm (500 ⁇ ).
- the coated wafer was then cured in an oven under nitrogen for 20 minutes at a temperature of 210 ° C + 5 ° C, and then the residue of the curing agent was removed by purging with deionized water for 5 minutes.
- the curing agent prevented the resist images from flowing sideways, and the dimensional changes of the images were small ( ⁇ 0.508 mm) ( ⁇ 20 microinches).
- the exposed areas of the metal layer were then etched by placing the wafer in a reactive gas plasma.
- the removal of the resist mask was uniform and the resist had a smooth surface after the metal etching process.
- This method makes it possible to use a thinner resist mask without attacking the parts of the metal layer lying under the mask during the plasma etching process.
- resist layers on comparison wafers which were only post-cured in the usual way or contained a peroxide additive in the composition, showed a rough surface with holes after the plasma etching.
- a mask pattern of a positive photoresist with a thickness of about 1.5 pm was, as indicated in Example 1, on a silicon wafer, the surface of which was coated with a therm mix oxide was coated, formed.
- the resist mask was coated using a solution of the sodium salt of 1-diazo-2-oxide-naphthalene-4-sulfonic acid in deionized water. About 4 to 6 ml of the solution, which was filtered through a 0.5 ⁇ m filter, was spun onto the resist images at a spinning speed of 3500 revolutions per minute within 1 minute. The wafer was then cured in an oven under a nitrogen atmosphere for 20 minutes at a temperature of 210 ° C + 5 ° C.
- Photomicrographs of the resist image showed that flow of the resist image was substantially avoided.
- resist images on control wafers which had not been subjected to the curing process according to the invention showed a strong flow after curing at 210 ° C.
- Resist images which had been treated with peroxides such as Lupersol 101 (2,5-dimethyl-2,5-di (tert-butyl-peroxy) hexane or polymethacrylic acid solutions in deionized water and had been post-cured for 20 minutes at 210 ° C. also showed strong flow and were deformed.
- silicon semiconductor wafers the surface of which was covered with a thermal oxide, were coated by spinning at 6000 revolutions per minute with a resist layer which consisted of a partially cyclized poly-cis-isoprene polymer and 2. 6-bis (p-azido-benzylidene) -4 - methylcyclohexane as a sensitizer.
- the layer was precured at 90 ° C for 20 minutes and then imagewise exposed to ultraviolet light for 1 minute.
- the exposed wafers were developed in a solvent at room temperature for 4 minutes to remove the unexposed areas and blown dry with nitrogen.
- the wafer was then split in half and one half was washed with an aqueous solution containing 4.3% by weight of the sodium salt of 2-diazo-1-oxide-naphthalene-5-sulfonic acid and 0.1% by weight. Polymethacrylic acid coated. The other half was used for the control measurement. Both halves of the wafer were cured for 30 minutes in a nitrogen atmosphere in an oven at 180 ° C. The treated resist image showed a significantly improved dimensional stability of the image after curing. The resist image on the untreated half was severely melted. Similar results were obtained with another wafer, one half of which was treated and the other half of which was not treated, and both halves had been cured under nitrogen at 210 ° C for 30 minutes.
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung einer fließbeständigen Resistmaske. Resistmasken werden, damit sie bei den während nachfolgende, Prozeßschritte zur Anwendung kommenden höheren Temperaturen fließbeständig bleiben, mit einem Härtungsmittel vom o-Chinondiazidtyp, insbesondere mit o-Chinondiazidsulfonsäuren oder Carbonsäuren beschichtet und auf eine Temparatur zwischen 110 und 210°C erhitzt, um eine Reaktion des Härtungsmittels mit dem Resist herbeizuführen. die Anwendung des Härtungsmittels erfolgt in Form einer wässrigen oder wässrig-alkoholischen Lösung mit einem Gehalt an 0,5 bis 10 Gew.%, bezogen auf das Gesamtgewicht der Lösung.The invention relates to a method for producing a flow-resistant resist mask. Resist masks are coated with a hardening agent of the o-quinonediazide type, in particular with o-quinonediazide sulfonic acids or carboxylic acids, and heated to a temperature between 110 and 210 ° C in order to ensure that they remain flow-resistant at the higher temperatures used in subsequent process steps, and heated to a temperature between 110 and 210 ° C in order to react of the curing agent with the resist. the hardening agent is used in the form of an aqueous or aqueous-alcoholic solution containing 0.5 to 10% by weight, based on the total weight of the solution.
Description
Die Ausbildung von Resistmasken bei der Herstellung integrierter Schaltkreise unter Verwendung strahlungsempfindlicher Schichten mit einem Gehalt an verschiedenen organischen Polymeren ist bekannt. Schichten aus einem strahlungsempfindlichen Material werden auf eine Unterlage aufgetragen, Licht oder einer anderen aktivierenden Strahlung wie Elektronenstrahlen oder Röntgenstrahlen in einem bildmäßigen Muster ausgesetzt und zu einem sichtbaren Bild entwickelt durch Entfernen der löslicheren Anteile der Schicht in einer Entwicklerlösung. Um die Eigenschaften der zurückbleibenden Teile der Resistschicht zu verbessern, beispielsweise der Adhäsion zu verschie- denen Unterlagen, ihre Widerstandsfähigkeit gegen chemischen und/oder thermischen Abbau, wird das Resistmuster in üblicher Weise bei einer erhöhten Temperatur nachgehärtet. Die thermoplastischen Polymermaterialien in dem Resist fließen bei Temperaturen, die über deren Glasübergangstemperatur liegen. Diese Tendenz zum Fließen deformiert das Resistbildmuster, und bei den hochaufgelösten Mustern, welche beispielsweise zur Herstellung integrierter Schaltkreise erforderlich sind, kann diese Verformung zu Dimensionsänderungen oder sogar zum Zusammenfließen der feinen Linien führen. Eine solche Verformung kann auch stattfinden, wenn das Resistbild während eines Prozeßschritts, durchgeführt am Substrat, erhitzt wird, beispielsweise bei Anwendung heißer Ätzlösungen, Ionenimplantation oder Plasmaätzen. Um diesen Nachteil zu beseitigen, wurden dem Photoresist freie Radikalbildner einverleibt, wie beispielsweise in der deutschen Offenlegungsschrift 2 518 480 beschrieben ist. Mit diesem Verfahren werden zwar Resistmasken mit verbesserter chemischer und thermischer Beständigkeit erhalten, gleichzeitig wird jedoch auch die Strahlungsempfindlichkeit der Resistmaterialien herabgesetzt, so daß längere Belichtungszeiten erforderlich sind. In der US-Patentschrift 3 920 483 wird ein Resisthärtungsprozeß zur Anwendung vor der Ionenimplantation beschrieben, bei dem die Resistmaske einer Hochfrequenz-Gasplasmaoxidation unterworfen wird, um die Dikke der Photoresistschicht herabzusetzen und das Fließen des Resists während der Ionenimplantation zu begrenzen.The formation of resist masks in the manufacture of integrated circuits using radiation-sensitive layers containing various organic polymers is known. Layers of a radiation sensitive material are applied to a support, exposed to light or other activating radiation such as electron beams or X-rays in an imagewise pattern and developed into a visible image by removing the more soluble portions of the layer in a developer solution. In order to improve the properties of the remaining parts of the resist layer, for example the adhesion to various substrates, their resistance to chemical and / or thermal degradation, the resist pattern is post-cured in the usual way at an elevated temperature. The thermoplastic polymer materials in the resist flow at temperatures above their glass transition temperature. This tendency to flow deforms the resist pattern, and in the high-resolution patterns that are required, for example, to manufacture integrated circuits, this deformation can result in dimensional changes or even cause the fine lines to flow together. Such deformation can also take place if the resist image is heated during a process step carried out on the substrate, for example when using hot etching solutions, ion implantation or plasma etching. In order to overcome this disadvantage, free radical formers were incorporated into the photoresist, as described, for example, in German Offenlegungsschrift 2,518,480. With this method, resist masks with improved chemical and thermal resistance are obtained, but at the same time the radiation sensitivity of the resist materials is reduced, so that longer exposure times are required. U.S. Patent No. 3,920,483 describes a pre-ion implant resist curing process in which the resist mask is subjected to high frequency gas plasma oxidation to reduce the thickness of the photoresist layer and limit the flow of the resist during ion implantation.
Aufgabe der Erfindung ist ein Verfahren zur Herstellung einer fließbeständigen Resistmaske durch Härten, bei dem keine besondere Einrichtung für den Härtungsprozeß erforderlich ist und bei dem die Resistzusammensetzung vor der Belichtung nicht modifiziert zu werden braucht.The object of the invention is a method for producing a flow-resistant resist mask by curing, in which no special device is required for the curing process and in which the resist composition does not have to be modified before exposure.
Die Aufgabe der Erfindung wird gelöst durch ein Verfahren der eingangs genannten Art, das dadurch gekennzeichnet ist, daß auf eine Resistmaske ein Härtungsmittel vom o-Chinondiazidtyp aufgetragen, die beschichtete Maske erhitzt und dann dab überschüssige Härtungsmittel entfernt wird.The object of the invention is achieved by a method of the type mentioned at the outset, which is characterized in that a curing agent of the o-quinonediazide type is applied to a resist mask, the coated mask is heated and then excess curing agent is removed therefrom.
Vorteilhafte Ausführungsformen der Erfindung sind in den Unteransprüchen niedergelegt.Advantageous embodiments of the invention are laid down in the subclaims.
Die Härtungsmittel zur Anwendung in dem erfindungsgemäßen Verfahren sind wasserlösliche Salze der o-Chinondiazidsulfon- und Carbonsäuren. Verbindungen dieser Art schließen o-Chinondiazide der Benzol-, Naphthalin- und Phenanthren-Reine ein. Beispiele der Verbindungen haben die nachfolgend angegebenen Formeln:
Beispiele spezieller Verbindungen sind:
- Das Natriumsalz der Benzol-2,1-diazo-oxid-4-sulfonsäure, das Natriumsalz der Naphthalin-1,2-diazo-oxid-4-sulfonsäure, das Kaliumsalz der Naphthalin-1,2-diazo-oxid-4-carbonsäure, das Natriumsalz der Naphthalin-2,1-diazo-oxid-5-sulfonsäure, das Natriumsalz der 1,2-Diazo-phenanthrol-(2)-x-sulfonsäure. Die Beschichtungslösungen der Härtungsmittel werden in solchen Konzentrationen hergestellt, daß etwa 0,5 bis 10 Gew.% des Härtungsmittels, bezogen'auf das Gesamtgewicht der Lösung vorhanden ist. Konzentrationen unter 0,5 Gew.% bewirken unter Umständen eine nicht ausreichende Härtung zur Verhinderung des Resistfließens beim Erhitzen. Es werden auch keine besonderen Vorteile erhalten bei Anwendung von Mengen, die größer als 1O Gew.% sind, und die Anwesenheit solcher Mengen kann zu Krater-oder Blasenbildung, verursacht durch die Gasentwicklung während des Erhitzens, in dem Resistmaskenmuster führen.
- The sodium salt of benzene-2,1-diazo-oxide-4-sulfonic acid, the sodium salt of naphthalene-1,2-diazo-oxide-4-sulfonic acid, the potassium salt of naphthalene-1,2-diazo-oxide-4-carboxylic acid , the sodium salt of naphthalene-2,1-diazo-oxide-5-sulfonic acid, the sodium salt of 1,2-diazo-phenanthrol- (2) -x-sulfonic acid. The coating solutions of the curing agents are prepared in such concentrations that about 0.5 to 10% by weight of the curing agent, based on the total weight of the solution, is present. Concentrations below 0.5% by weight may cause insufficient hardening to prevent the resist from flowing when heated. Also, no particular advantages are obtained using amounts greater than 10% by weight, and the presence of such amounts can cause crater or bubble formation in the resist mask pattern caused by gas evolution during heating.
In der Praxis sollten die Konzentrationen, wenn Resistschichtflächen ohne Muster größer als 0,508 x 0,508 mm (20 x 20 mils) vorhanden sind, in einem Bereich von etwa 0,5 bis 1,5 Gew.% gehalten werden, um die Kraterbildung in diesen durchgehenden Bereichen zu vermeiden.In practice, when resist layer areas with no pattern are larger than 0.508 x 0.508 mm (20 x 20 mils), the concentrations should be kept in a range of about 0.5 to 1.5% by weight to prevent crater formation therein Areas to avoid.
Das Lösungsmittelsystem oder das Härtungsmittel ist auf wässriger Basis, damit ein Angriff der Resistschicht durch die Beschichtungslösung vermieden wird. Es wurde gefunden, daß die Resistschicht durch die Beschichtungslösung besser benetzt wird und demzufolge ein einheitlicherer Überzug des Härtungsmittels erhalten wird, wenn eine Mischung von Wasser mit Alkoholen mit 2 bis 4 Kohlen stoffatomen, beispielsweise mit Äthanol, Propanol oder Butanol verwendet wird. Die Anteile von Wasser und Alkohol werden so gewählt, daß eine ausreichende Löslichkeit des Härtungsmittels erhalten und gleichzeitig ein Angriff des Lösungsmittels auf das Resistsystem vermieden wird. Anstelle oder zusätzlich zu den Alkoholen können zur Verbesserung der Benetzung oberflächenaktive Mittel in Mengen von etwa 0,01 bis 1 Gew.% zugesetzt werden. Beispiele brauchbarer oberflächenaktiver Mittel sind Natriumlaurylsulfat, oberflächenaktive Mittel auf Fluorkohlenwasserstoffbasis, Natriumpalmitat und Polymethacrylsäurelösungen.The solvent system or the hardening agent is water-based, so that attack of the resist layer by the coating solution is avoided. It has been found that the resist layer is better wetted by the coating solution and consequently a more uniform coating of the hardening agent is obtained when a mixture of water with alcohols with 2 to 4 carbon atoms, for example with ethanol, propanol or butanol, is used. The proportions of water and alcohol are chosen so that sufficient solubility of the hardening agent is obtained and at the same time an attack by the solvent on the resist system is avoided. Instead of or in addition to the alcohols, surfactants can be added in amounts of about 0.01 to 1% by weight to improve the wetting. Examples of useful surfactants are sodium lauryl sulfate, fluorine surfactants hydrocarbon base, sodium palmitate and polymethacrylic acid solutions.
Das Härtungsmittel wird auf die Resistmaske mittels konventioneller Verfahren, beispielsweise durch Tauchen, Sprühen oder Verspinnen aufgetragen unter Erhalt einer kontinuierlichen Schicht über der Resistmaske und der Unterlage. Eine Schichtdicke von etwa 40 nm (400 Å) ist als Minimum erforderlich, um einen kontinuierlichen Überzug auf der Oberfläche und den Seitenwänden des Resistbildes zu erhalten. Eine Schichtdicke von etwa 50 bis 100 nm (500 bis 1000 Å) wird bevorzugt. Die gewünschte Schichtdicke kann bei der Technik des Verspinnens durch Variation der Spinngeschwindigkeit erhalten werden. Die Spinnzeit wird so gewählt, daß ein Großteil des Lösungsmittels durch Verdampfen entfernt wird.The curing agent is applied to the resist mask by conventional methods, for example by dipping, spraying or spinning, to obtain a continuous layer over the resist mask and the base. A layer thickness of about 40 nm (400 Å) is required as a minimum in order to obtain a continuous coating on the surface and the side walls of the resist image. A layer thickness of about 50 to 100 nm (500 to 1000 Å) is preferred. The desired layer thickness can be obtained in the spinning technique by varying the spinning speed. The S pinnzeit is chosen so that a major part of the solvent is removed by evaporation.
Die Resistzusammensetzungen, welche mit dem erfindungsgemäßen Verfahren gehärtet werden können, können entweder positiv oder negativ arbeitende Resistmaterialien sein. Negative Resistmaterialien sind solche, die, wenn sie bestrahlt werden, vernetzen und weniger löslich werden. Beispiele negativer Resistmaterialien sind sensibilisierte Polyvinylcinnamat-Polymerzusammensetzungen, die beispielsweise in der US-Patentschrift 2 732 301 beschrieben sind und sensibilisierte, teilcyclisierte Poly-cisisopren-Polymerzusammensetzungen, die beispielsweise in er US-Patentschrift 2 852 379 beschrieben sind. Beispiele positiver Resistmaterialien, welche unter Einwirkung von Strahlung abgebaut und dadurch mehr löslich werden, sind sensibilisierte Novolakharzzusammensetzungen, die beispielsweise in den US-Patentschriften 3 046 118, 3 046 121, 3 201 239 und 3 666 743 beschrieben sind.The resist compositions which can be cured by the process according to the invention can be either positive or negative resist materials. Negative resist materials are those that, when irradiated, crosslink and become less soluble. Examples of negative resist materials are sensitized polyvinyl cinnamate polymer compositions described, for example, in U.S. Patent 2,732,301 and sensitized, partially cyclized poly-cisisoprene polymer compositions described, for example, in U.S. Patent 2,852,379. Examples of positive resist materials which degrade under the action of radiation and thereby become more soluble are sensitized novolak resin compositions which are described, for example, in US Pat. Nos. 3,046,118, 3,046,121, 3,201,239 and 3,666,743.
Die Resistschichten werden auf eine Unterlage aufgetragen und bildmäßig belichtet. Anschließend werden die löslicheren Bereiche der Schicht, die im Falle eines positiven Resists die belichteten Bereiche und im Falle eines negativen Resists die nichtbelichteten Bereiche sind, mit einer Entwicklerlösung entfernt. Das resultierende Resistmaskenmuster kann dann in dem erfindungsgemäßen Verfahren behandelt werden, indem es mit einer Schicht eines o-Chinondiazid-Härtungsmittels bedeckt wird. Nach dem Beschichten wird die Resistmaske auf eine Temperatur erhitzt, die ausreichend ist, um eine Reaktion des o-Chinondiazids mit der Resistschicht herbeizuführen unter Ausbildung einer vernetzten äußeren Schicht, insbesondere an den Seitenwänden des Resistbildes, so daß das seitliche Fließen des Bildes verhindert wird, wenn das Bild auf Temperaturen erhitzt wird, die über den Glasübergangstemperaturen des Polymeranteils der Resistschicht liegen. Es werden Temperaturen in einem Bereich von etwa 110 bis 210 0C und eine inerte Atmosphäre, beispielsweise Stickstoffatmosphäre angewendet. Eine Härtung in einem Ofen wird bevorzugt, weil weniger Krater in relativ großen Resistschichtbereichen ohne Muster ausgebildet werden im Vergleich zur Härtung der Resistschicht auf einer Heizplatte. Härtungszeiten von 10 bis etwa 30 Minuten sind ausreichend, um die Härtung zu Ende zu führen.The resist layers are applied to a base and exposed imagewise. Then the more soluble areas of the layer, which are the exposed areas in the case of a positive resist and the unexposed areas in the case of a negative resist, are removed with a developer solution. The resulting resist mask pattern can then be treated in the process of the invention by covering it with a layer of an o-quinonediazide curing agent. After coating, the resist mask is heated to a temperature which is sufficient to bring about a reaction of the o-quinonediazide with the resist layer, with the formation of a crosslinked outer layer, in particular on the side walls of the resist image, so that the lateral flow of the image is prevented, when the image is heated to temperatures above the glass transition temperatures of the polymer portion of the resist layer. Temperatures in a range from approximately 110 to 210 ° C. and an inert atmosphere, for example a nitrogen atmosphere, are used. Curing in an oven is preferred because fewer craters are formed in relatively large areas of the resist layer without a pattern compared to curing the resist layer on a hot plate. Hardening times of 10 to about 30 minutes are sufficient to complete the hardening.
Nachdem die Härtung zu Ende geführt wurde, kann der Rückstand des Härtungsmittels, welches auf der Unterlage an den Rändern der Resistmaske zurückbleibt, durch Spülen mit Wasser leicht entfernt werden. Die resultierende Resistmaske zeigt kaum seitliches Fließen der Bilder. Das gehärtete Resistbild behält seine Dimensionen bei nachfolgenden Behandlungen der freigelegten Bereiche der Unterlage, beispielsweise beim Ätzen mit heißen Säuren oder mit einem reaktiven Gasplasma, bei der Ionenimplantation oder einem Metallaufdampfverfahren, bei denen die Resistschicht auf höhere Temperaturen erhitzt wird.After curing is complete, the residue of the curing agent which remains on the base at the edges of the resist mask can be easily removed by rinsing with water. The resulting resist mask shows little lateral flow of the images. The hardened resist image retains its dimensions during subsequent treatments of the exposed areas of the base, for example when hot etching Acids or with a reactive gas plasma, during ion implantation or a metal vapor deposition process, in which the resist layer is heated to higher temperatures.
Die Erfindung wird anhand der nachfolgenden Ausführungsbeispiele näher erläutert.The invention is explained in more detail using the following exemplary embodiments.
Ein Maskenmuster aus einem positiven Photoresist wurde auf der Oberfläche eines gereinigten, mit Metall beschichteten Siliciumhalbleiterwafers ausgebildet. Die Resistzusammensetzung bestand aus einem Phenolformaldehyd-Novolakharz und dem 2-Diazo-1-oxo-naphthalin-5-sulfonsäureester des Dihydroxybenzophenons. Der Resist wurde durch Verspinnen bei 4000 Umdrehungen pro Minute auf die Metalloberfläche aufgetragen, zu einer Trockenschichtdicke von etwa 2,2 pm 20 Minuten lang bei etwa 85 °C gehärtet und dann bildmäßig mit aktinischer Strahlung belichtet und mit einer wässrigen alkalischen Entwicklerlösung entwickelt, um die belichteten Bereiche zu entfernen. Auf die Resistmaske und den Wafer wurde durch Verspinnen bei 3000 Umdrehungen pro Minute innerhalb einer Minute eine 1 Gew.%ige Lösung des Natriumsalzes der 2-Diazo-1-oxid- naphthalin-5-sulfonsäure in einer Mischung aus Wasser und Isopropanol im Volumverhältnis 50:50 aufgetragen. Die Beschichtungsdicke betrug etwa 50 nm (500 Å). Der beschichtete Wafer wurde dann in einem Ofen unter Stickstoff 20 Minuten lang bei einer Temperatur von 210 °C + 5 °C gehärtet, und dann wurde der Rückstand des Härtungsmittéls durch ein 5 Minuten dauerndes Spülen mit deionisiertem Wasser entfernt. Das Härtungsmittel verhinderte ein seitliches Fließen der Resistbilder, und die Dimensionsänderungen der Bilder waren klein (≤ 0,508 mm) (≤ 20 microinches).A mask pattern of a positive photoresist was formed on the surface of a cleaned, metal-coated silicon semiconductor wafer. The resist composition consisted of a phenol formaldehyde novolak resin and the 2-diazo-1-oxo-naphthalene-5-sulfonic acid ester of dihydroxybenzophenone. The resist was applied to the metal surface by spinning at 4000 rpm, cured to a dry film thickness of about 2.2 pm for 20 minutes at about 85 ° C. and then imagewise exposed to actinic radiation and developed with an aqueous alkaline developer solution to remove the to remove exposed areas. A 1% by weight solution of the sodium salt of 2-diazo-1-oxide-naphthalene-5-sulfonic acid in a mixture of water and isopropanol in a volume ratio of 50 was applied to the resist mask and the wafer by spinning at 3000 revolutions per minute within one minute : 50 plotted. The coating thickness was about 50 nm (500 Å). The coated wafer was then cured in an oven under nitrogen for 20 minutes at a temperature of 210 ° C + 5 ° C, and then the residue of the curing agent was removed by purging with deionized water for 5 minutes. The curing agent prevented the resist images from flowing sideways, and the dimensional changes of the images were small (≤ 0.508 mm) (≤ 20 microinches).
Die freigelegten Bereiche der Metallschicht wurden dann geätzt, indem der Wafer in ein reaktives Gasplasma gegeben wurde. Die Abtragung der Resistmaske war einheitlich, und der Resist wies nach dem Metallätzverfahren eine glatte Oberfläche auf. Durch dieses Verfahren wird die 1 Anwendung einer dünneren Resistmaske möglich, ohne daß ein Angriff auf die unter der Maske liegenden Teile der Metallschicht während des Plasmaätzprozesses stattfindet. Im Gegensatz dazu zeigten Resistschichten auf Vergleichswafern, die nur in üblicher Weise nachgehärtet waren oder einen Peroxidzusatz in der Zusammensetzung enthielten, nach dem Plasmaätzen eine rauhe Oberfläche mit Löchern.The exposed areas of the metal layer were then etched by placing the wafer in a reactive gas plasma. The removal of the resist mask was uniform and the resist had a smooth surface after the metal etching process. This method makes it possible to use a thinner resist mask without attacking the parts of the metal layer lying under the mask during the plasma etching process. In contrast, resist layers on comparison wafers, which were only post-cured in the usual way or contained a peroxide additive in the composition, showed a rough surface with holes after the plasma etching.
Die Anwendung des Härtungsmittels in Konzentrationen im Bereich von 2,5 bis 5 Gew.% gemäß Beispiel 1 führte zu einer normalen Härtung des Photoresistmusters, aber große, 0,508 x 1,27 mm (20 bis 50 Mil)-Resistbereiche ohne Muster zeigten Krater, welche offensichtlich durch das Bersten eingeschlossener Gasblasen verursacht wurden, die während des Härtungsverfahrens gebildet worden waren. Bei Anwendung einer Härtungsmittelkonzentration von 0,25 Gew.% bei der nur kleine Änderungen in der Bildgröße verursacht wurden, zeigte sich eine beachtliche Verdünnung der schmalen (etwa 2,54 mm ≙ 100 microinch) Resistlinien. Die optimale Härtungsmittelkonzentration sollte deshalb so gewählt werden, daß das Fließen auf ein Minimum herabgesetzt wird und gleichzeitig eine Kraterbildung in dem speziellen zu behandelnden Resistmuster vermieden wird. Konzentrationen von etwa 0,5 bis 1,25 Gew.% ergaben gute Gesamtergebnisse für integrierte Schaltkreismuster.Use of the curing agent in concentrations in the range of 2.5 to 5% by weight according to Example 1 led to normal curing of the photoresist pattern, but large, 0.508 x 1.27 mm (20 to 50 mil) resist areas without patterns showed craters, which was apparently caused by the rupture of trapped gas bubbles formed during the curing process. When using a hardener concentration of 0.25% by weight, with which only small changes in the image size were caused, there was a considerable thinning of the narrow (about 2.54 mm ch 100 microinch) resist lines. The optimum hardener concentration should therefore be chosen so that the flow is reduced to a minimum and at the same time crater formation in the special resist pattern to be treated is avoided. Concentrations of about 0.5 to 1.25% by weight gave good overall results for integrated circuit patterns.
Ein Maskenmuster aus einem positiven Photoresist mit einer Dicke von etwa 1,5 pm wurde, wie in Beispiel 1 angegeben, auf einem Siliciumwafer, dessen Oberfläche mit einem thermischen Oxid beschichtet war, ausgebildet. Die Resistmaske wurde beschichtet unter Verwendung einer Lösung des Na- triumsalzes der 1-Diazo-2-oxid-naphthalin-4-sulfonsäure in deionisiertem Wasser. Ungefähr 4 bis 6 ml der Lösung, welche durch ein 0,5 µm Filter filtriert war, wurde innerhalb 1 Minute auf die Resistbilder mit einer Spinngeschwindigkeit von 3500 Umdrehungen pro Minute aufgesponnen. Der Wafer wurde dann in einem Ofen unter Stickstoffatmosphäre 20 Minuten lang bei einer Temperatur von 210 °C + 5 °C gehärtet. Mikrophotographien des Resistbildes zeigten, daß ein Fließen des Resistbildes im wesentlichen vermieden wurde. Im Gegensatz dazu zeigten Resistbilder auf Kontrollwafern, welche dem erfindungsgemäßen Härtungsverfahren nicht unterworfen worden waren, ein starkes Fließen nach einem Härten bei 210 °C. Resistbilder, welcher mit Peroxiden wie Lupersol 101 (2,5-Dimethyl- 2,5-di(tert-butyl-peroxy)-hexan oder Polymethacryl- säurelösungen in deionisiertem Wasser behandelt und 20 Minuten bei 210 °C nachgehärtet worden waren, zeigten auch starkes Fließen und waren deformiert.A mask pattern of a positive photoresist with a thickness of about 1.5 pm was, as indicated in Example 1, on a silicon wafer, the surface of which was coated with a therm mix oxide was coated, formed. The resist mask was coated using a solution of the sodium salt of 1-diazo-2-oxide-naphthalene-4-sulfonic acid in deionized water. About 4 to 6 ml of the solution, which was filtered through a 0.5 μm filter, was spun onto the resist images at a spinning speed of 3500 revolutions per minute within 1 minute. The wafer was then cured in an oven under a nitrogen atmosphere for 20 minutes at a temperature of 210 ° C + 5 ° C. Photomicrographs of the resist image showed that flow of the resist image was substantially avoided. In contrast, resist images on control wafers which had not been subjected to the curing process according to the invention showed a strong flow after curing at 210 ° C. Resist images which had been treated with peroxides such as Lupersol 101 (2,5-dimethyl-2,5-di (tert-butyl-peroxy) hexane or polymethacrylic acid solutions in deionized water and had been post-cured for 20 minutes at 210 ° C. also showed strong flow and were deformed.
Um die Anwendung des erfindungsgemäßen Verfahrens auf negativ arbeitende Resistmaterialien zu zeigen, wurden Siliciumhalbleiterwafer, deren Oberfläche mit einem thermischen Oxid bedeckt war, mittels Verspinnen bei 6000 Umdrehungen pro Minute mit einer Resistschicht beschichtet,welche aus einem teilweise cyclisierten Poly-cis-isoprenpolymeren und 2,6-Bis-(p-azido-benzyliden)-4-methylcyclohexan als Sensibilisator bestand. Die Schicht wurde 20 Minuten lang bei 90 °C vorgehärtet und dann 1 Minute lang mit ultraviolettem Licht bildweise belichtet. Die belichteten Wafer wurden 4 Minuten lang bei Zimmertemperatur in einem Lösungsmittel entwickelt, um die nichtbelichteten Bereiche zu entfernen und mit Stickstoff trockengeblasen. Der Wafer wurde dann in zwei Hälften geteilt, und eine Hälfte wurde mit einer wässrigen Lösung mit einem Gehalt an 4,3 Gew.% des Natriumsalzes der 2-Diazo-1-oxid-naphthalin-5-sulfonsäure und 0,1 Gew.% Polymethacrylsäure beschichtet. Die andere Hälfte wurde zur Kontrollmessung verwendet. Beide Waferhälften wurden 30 Minuten in einer Stickstoffatmosphäre in einem Ofen bei 180 °C gehärtet. Das behandelte Resistbild zeigte nach der Härtung eine wesentliche verbesserte Dimensionsstabilität des Bildes. Das Resistbild auf der nichtbehandelten Hälfte war stark zerflossen. Ähnliche Ergebnisse wurden mit einem anderen Wafer erhalten, dessen eine Hälfte behandelt und die andere Hälfte nicht behandelt war und beide Hälften 30 Minuten lang unter Stickstoff bei 210 °C gehärtet worden waren.In order to show the application of the method according to the invention to negative-working resist materials, silicon semiconductor wafers, the surface of which was covered with a thermal oxide, were coated by spinning at 6000 revolutions per minute with a resist layer which consisted of a partially cyclized poly-cis-isoprene polymer and 2. 6-bis (p-azido-benzylidene) -4 - methylcyclohexane as a sensitizer. The layer was precured at 90 ° C for 20 minutes and then imagewise exposed to ultraviolet light for 1 minute. The exposed wafers were developed in a solvent at room temperature for 4 minutes to remove the unexposed areas and blown dry with nitrogen. The wafer was then split in half and one half was washed with an aqueous solution containing 4.3% by weight of the sodium salt of 2-diazo-1-oxide-naphthalene-5-sulfonic acid and 0.1% by weight. Polymethacrylic acid coated. The other half was used for the control measurement. Both halves of the wafer were cured for 30 minutes in a nitrogen atmosphere in an oven at 180 ° C. The treated resist image showed a significantly improved dimensional stability of the image after curing. The resist image on the untreated half was severely melted. Similar results were obtained with another wafer, one half of which was treated and the other half of which was not treated, and both halves had been cured under nitrogen at 210 ° C for 30 minutes.
Es wurde ein Härtungsverfahren für Resistmasken beschrieben, für welches keine besonderen Apparaturen oder Zusätze zu der Resistschicht vor Ausbildung der Resistmaske erforderlich sind.A curing process for resist masks has been described, for which no special apparatus or additives to the resist layer are required before the resist mask is formed.
Claims (7)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/822,468 US4125650A (en) | 1977-08-08 | 1977-08-08 | Resist image hardening process |
| US822468 | 1977-08-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0000702A1 true EP0000702A1 (en) | 1979-02-21 |
| EP0000702B1 EP0000702B1 (en) | 1981-10-07 |
Family
ID=25236122
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP78100337A Expired EP0000702B1 (en) | 1977-08-08 | 1978-07-10 | Process for forming a flow-resistant resist mask of radioation-sensitive material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4125650A (en) |
| EP (1) | EP0000702B1 (en) |
| JP (1) | JPS5429574A (en) |
| DE (1) | DE2861132D1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180037973A1 (en) * | 2016-08-08 | 2018-02-08 | Mt2, Llc | Method for the treatment of metallic particles and objects contaminated with metallic particles |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187331A (en) * | 1978-08-24 | 1980-02-05 | International Business Machines Corp. | Fluorine plasma resist image hardening |
| US4259369A (en) * | 1979-12-13 | 1981-03-31 | International Business Machines Corporation | Image hardening process |
| DE3022362A1 (en) * | 1980-06-14 | 1981-12-24 | Hoechst Ag, 6000 Frankfurt | LIGHT-SENSITIVE COPYING MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
| US4343876A (en) * | 1980-11-21 | 1982-08-10 | E. I. Du Pont De Nemours And Company | Dot-enlargement process for photopolymer litho masks |
| JPS5844715A (en) * | 1981-09-11 | 1983-03-15 | Fujitsu Ltd | Forming method for minute pattern |
| US4439516A (en) * | 1982-03-15 | 1984-03-27 | Shipley Company Inc. | High temperature positive diazo photoresist processing using polyvinyl phenol |
| GB2121197A (en) * | 1982-05-26 | 1983-12-14 | Philips Electronic Associated | Plasma-etch resistant mask formation |
| DE3325022A1 (en) * | 1983-07-11 | 1985-01-24 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING NEGATIVE COPIES BY MEANS OF A MATERIAL BASED ON 1,2-CHINONDIAZIDES |
| US4568631A (en) * | 1984-04-30 | 1986-02-04 | International Business Machines Corporation | Process for delineating photoresist lines at pattern edges only using image reversal composition with diazoquinone |
| KR930010248B1 (en) * | 1984-09-14 | 1993-10-15 | 가부시끼가이샤 히다찌세이사꾸쇼 | Process for pattern forming |
| US4596763A (en) * | 1984-10-01 | 1986-06-24 | American Hoechst Corporation | Positive photoresist processing with mid U-V range exposure |
| GB2170015A (en) * | 1985-01-11 | 1986-07-23 | Philips Electronic Associated | Method of manufacturing a semiconductor device |
| US4981909A (en) * | 1985-03-19 | 1991-01-01 | International Business Machines Corporation | Plasma-resistant polymeric material, preparation thereof, and use thereof |
| US4782008A (en) * | 1985-03-19 | 1988-11-01 | International Business Machines Corporation | Plasma-resistant polymeric material, preparation thereof, and use thereof |
| US4908298A (en) * | 1985-03-19 | 1990-03-13 | International Business Machines Corporation | Method of creating patterned multilayer films for use in production of semiconductor circuits and systems |
| CA1282273C (en) * | 1985-03-19 | 1991-04-02 | International Business Machines Corporation | Method of creating patterned multilayer films for use in production of semiconductor circuits and systems |
| US4777111A (en) * | 1985-06-03 | 1988-10-11 | Fairmount Chemical Company, Inc. | Photographic element with diazo contrast enhancement layer and method of producing image in underlying photoresist layer of element |
| US4672021A (en) * | 1985-06-03 | 1987-06-09 | Fairmount Chemical Company | Contrast enhancement layer composition with naphthoquinone diazide, indicator dye and polymeric binder |
| US4701390A (en) * | 1985-11-27 | 1987-10-20 | Macdermid, Incorporated | Thermally stabilized photoresist images |
| EP0247153A4 (en) * | 1985-11-27 | 1988-05-19 | Macdermid Inc | Thermally stabilized photoresist images. |
| US4762768A (en) * | 1986-01-29 | 1988-08-09 | Macdermid, Incorporated | Thermally stabilized photoresist images |
| US4737425A (en) * | 1986-06-10 | 1988-04-12 | International Business Machines Corporation | Patterned resist and process |
| US4806455A (en) * | 1987-04-03 | 1989-02-21 | Macdermid, Incorporated | Thermal stabilization of photoresist images |
| DE3800176A1 (en) * | 1988-01-07 | 1989-07-20 | Bosch Gmbh Robert | CONTROL DEVICE FOR AN INTERNAL COMBUSTION ENGINE AND METHOD FOR SETTING PARAMETERS OF THE DEVICE |
| US6503693B1 (en) * | 1999-12-02 | 2003-01-07 | Axcelis Technologies, Inc. | UV assisted chemical modification of photoresist |
| DE10101734C2 (en) * | 2001-01-16 | 2003-04-24 | Osram Opto Semiconductors Gmbh | Method for forming an etching mask on a substrate |
| US6605413B1 (en) * | 2001-03-29 | 2003-08-12 | Advanced Micro Devices, Inc. | Chemical treatment to strengthen photoresists to prevent pattern collapse |
| US7314691B2 (en) * | 2004-04-08 | 2008-01-01 | Samsung Electronics Co., Ltd. | Mask pattern for semiconductor device fabrication, method of forming the same, method for preparing coating composition for fine pattern formation, and method of fabricating semiconductor device |
| US9563122B2 (en) | 2015-04-28 | 2017-02-07 | International Business Machines Corporation | Method to harden photoresist for directed self-assembly processes |
| US9659824B2 (en) | 2015-04-28 | 2017-05-23 | International Business Machines Corporation | Graphoepitaxy directed self-assembly process for semiconductor fin formation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU451978A1 (en) * | 1973-02-19 | 1974-11-30 | Предприятие П/Я А-7850 | Positive photoresist |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3278305A (en) * | 1963-07-12 | 1966-10-11 | Gevaert Photo Prod Nv | Photochemical cross-linking of polymers |
| GB1136544A (en) * | 1966-02-28 | 1968-12-11 | Agfa Gevaert Nv | Photochemical cross-linking of polymers |
| US3459708A (en) * | 1967-01-18 | 1969-08-05 | Chevron Res | Phenol-aldehyde wood bonding adhesives incorporating organic hydroperoxides and having improved curing rates |
| US3660097A (en) * | 1969-11-28 | 1972-05-02 | Polychrome Corp | Diazo-polyurethane light-sensitive compositions |
| US3711287A (en) * | 1971-05-19 | 1973-01-16 | Eastman Kodak Co | Photoresist compositions |
| US3920483A (en) * | 1974-11-25 | 1975-11-18 | Ibm | Method of ion implantation through a photoresist mask |
| JPS53115301A (en) * | 1977-03-17 | 1978-10-07 | Toppan Printing Co Ltd | Method of treating hard film of water soluble photoresist pattern |
-
1977
- 1977-08-08 US US05/822,468 patent/US4125650A/en not_active Expired - Lifetime
-
1978
- 1978-07-07 JP JP8217678A patent/JPS5429574A/en active Granted
- 1978-07-10 EP EP78100337A patent/EP0000702B1/en not_active Expired
- 1978-07-10 DE DE7878100337T patent/DE2861132D1/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU451978A1 (en) * | 1973-02-19 | 1974-11-30 | Предприятие П/Я А-7850 | Positive photoresist |
Non-Patent Citations (2)
| Title |
|---|
| CHEMICAL ABSTRACTS, Band 82, 1975, Columbus, Ohio (USA) A.I. PARAMONOV et al.: "Positive photoresist", Seite 486, Zusammenfassung Nr. 163064f; & SU-A-451 978 * |
| IBM TECHNICAL DISCLOSURE BULLETIN, Band 18, Nr. 5, Oktober 1975, Armonk, New York, B. BERGIN et al.: "Single layer optical lift-off process" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180037973A1 (en) * | 2016-08-08 | 2018-02-08 | Mt2, Llc | Method for the treatment of metallic particles and objects contaminated with metallic particles |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0000702B1 (en) | 1981-10-07 |
| JPS5429574A (en) | 1979-03-05 |
| JPS5649452B2 (en) | 1981-11-21 |
| US4125650A (en) | 1978-11-14 |
| DE2861132D1 (en) | 1981-12-17 |
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