Photoresist with rare-earth sensitizers

Abstract

A method of making a photoresist with rare-earth sensitizers is provided. The rare-earth sensitizer could be a salt or a rare-earth complex. According to the invention, photoresist composition is useful to pattern circuits by visible light.

Claims

1. A photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light, which comprises: (a) about 0.1 to about 10% by weight of a rare earth (RE) complex as a sensitizer in which a rare earth ion is encapsulated by organic ligands, the RE complex sensitizer selected from the group consisting of a RE picolinate, an RE lissamine, a RE(fod).sub.3 wherein fod is 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate, a RE(TTA).sub.3 Phen wherein TTA is theonyltrifluoroacetone and Phen is 1,10-phenanthroline, a RE(DBM).sub.3 Phen wherein DBM is dibenzoylmethane and Phen is 1,10-phenanthroline, and a RE fulleride; and (b) an ultraviolet, deep ultraviolet or extreme ultraviolet photoresist wherein the RE complex encapsulated by organic ligands is dissolved in the photoresist.

2. The photoresist composition having a quantum multiphoton confinement effect, defined in claim 1 wherein the rare earth in the RE complex is selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.

3. The photoresist composition having a quantum multiphoton confinement effect, defined in claim 1 wherein the RE complex is Eu(fod).sub.3.

4. The photoresist composition having a quantum multiphoton confinement effect, defined in claim 1 wherein the photoresist is a positive photoresist.

5. The photoresist composition having a quantum multiphoton confinement effect, defined in claim 4 wherein the positive photoresist is a novolac resin/quinone diazide type photoresist.

6. The photoresist composition having a quantum multiphoton confinement effect, defined in claim 1 wherein the photoresist is a negative photoresist.

7. A method of making the photoresist composition having a quantum multiphoton confinement effect, defined in claim 1 and which is capable of forming an image when exposed to visible light, which comprises: about 0.1 to about 10% by weight of the RE complex sensitizer in which a rare earth ion is encapsulated by organic ligands; and an ultraviolet, deep ultraviolet or extreme ultraviolet photoresist wherein the RE complex is dissolved in the photoresist, which comprises the steps of: (a) dissolving an ultraviolet, deep ultraviolet, or extreme ultraviolet photoresist in an organic solvent; (b) adding and mixing a quantity of the RE complex as a sensitizer in which a rare earth ion is encapsulated by organic ligands, soluble in the organic solvent; and (c) casting the photoresist composition as a film.

8. The method defined in claim 4 wherein the organic solvent is a single organic solvent or a mixture of organic solvents selected from the group consisting of acetone, methyl-ethyl-ketone, cyclohexanone, benzene, chlorobenzene, toluene, glycol ethers, isopropyl alcohol, ethanol and methanol.

9. An optical nanolithography system comprising: a photoresist having a quantum multiphoton confinement effect; a rare earth (RE) complex selected from the group consisting of a RE picolinate, a RE lissamine, a RE(fod).sub.3 wherein fod is 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate, a RE(TTA).sub.3 Phen wherein TTA is theonyltrifluoroacetone and Phen is 1,10-phenanthroline, a RE(DBM).sub.3 Phen wherein DBM is dibenzoylmethane and Phen is 1,10-phenanthroline, and a RE fulleride as a sensitizer for the photoresist; and at least one laser beam directed at said photoresist and adapted to write patterns to said photoresist.

10. The optical nanolithography system defined in claim 9 wherein the photoresist is an ultraviolet, deep ultraviolet or extreme ultraviolet photoresist with the RE complex as the sensitizer.

11. A method of making a photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light, which comprises: (a) about 0.1 to about 10% by weight of a rare earth (RE) complex as a sensitizer in which a rare earth ion is encapsulated by organic ligands, the RE complex sensitizer selected from the group consisting of an RE acetylacetonate, a RE picolinate, an RE lissamine, a RE(fod).sub.3 wherein fod is 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionate, a RE(TTA).sub.3 Phen wherein TTA is theonyltrifluoroacetone and Phen is 1,10-phenanthroline, a RE(DBM).sub.3 Phen wherein DBM is dibenzoylmethane and Phen is 1,10-phenanthroline, and a RE fulleride; and (b) an ultraviolet, deep ultraviolet or extreme ultraviolet photoresist wherein the RE complex encapsulated by organic ligands is dissolved in the photoresist, which comprises the step of incorporating the RE complex sensitizer directly into a monomer phase of an ultraviolet, deep ultraviolet, or extreme ultraviolet polymeric photoresist.

12. The method of making a photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light defined in claim 11 wherein the RE complex sensitizer is a RE acetylacetonate complex.

13. The method of making a photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light defined in claim 11 wherein the RE in the RE complex sensitizer is selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.

14. A photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light, which comprises: (a) about 0.1 to about 10% by weight of a rare earth (RE) salt selected from the group which consists of: naphthenate, stearate, lactate, citrate, and butoxide as a sensitizer; and (b) an ultraviolet, deep ultraviolet or extreme ultraviolet photoresist wherein the RE salt is dissolved in the photoresist wherein the photoresist is a positive photoresist.

15. The photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light defined in claim 14 wherein the positive photoresist is a novolac resin/quinone diazide type photoresist.

16. The photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light defined in claim 14 wherein the RE in the RE salt is selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb salts.

17. A photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light, which comprises: (a) about 0.1 to about 10% by weight of a rare earth (RE) salt selected from the group which consists of: stearate, lactate, citrate, and butoxide as a sensitizer; and (b) an ultraviolet, deep ultraviolet or extreme ultraviolet photoresist wherein the RE salt is dissolved in the photoresist wherein the photoresist is a positive or a negative photoresist.

18. The photoresist composition having a quantum multiphoton confinement effect and which is capable of forming an image when exposed to visible light defined in claim 17 wherein the RE in the RE salt is selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb salts.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(1) The present invention is described in further detail in the following examples which are given for illustrative purposes only. A method to produce a photoresist with rare-earth sensitizers consists in mixing two solutions with a single component (UV/DUV/EUV photoresist or rare-earth compound) soluble in the same organic solvent. Any solvents which are not photoreactive and which dissolve both components can be used in this invention.

(2) Positive photoresists comprising an alkali-soluble novolac resin and a quinone diazide as a sensitizer are well known in the art. It is generally the case that the novolac resin and quinone diazide are dissolved in an organic solvent. Suitable solvents include, but are not limited to acetone, methyl ethyl ketone, cyclohexanone, benzene, chlorobenzene, toluene, glycol ethers, isopropyl alcohol, ethanol and methanol. These solvents can be used individually or as mixtures thereof.

(3) A different way to incorporate rare-earth ions in photoresists is the encapsulation of the ions by complexation with organic ligands.

EXAMPLE 1

(4) A novolac resin/quinone diazide type photoresist and Eu naphthenate are dissolved separately in acetone. Both solutions were mixed to obtain the final composition: novolac resin/quinone diazide type photoresist (18 wt. %), Eu naphthenate (3 wt. %) and acetone (79 wt. %). The photoresist composition was uniformly applied by using a spinner to the surface of a silicon wafer of 4 inches diameter. The coated wafers were then soft baked on a hotplate at 110 C. for 90 seconds. A green radiation (=532 nm), supplied by a frequency doubled Nd:YAG laser, was used to expose at 50 mJ/cm.sup.2 the coated wafers. Athereby completing an optical nano-lithography system comprising a photoresist having a quantum multi-photon confinement effect, and a laser directed to the photoresist and adapted to qrite patterns in the photoresist. The Ugra digital scale with lines and space widths of varying size, was used to provide a selective exposure pattern. The imaged wafers were developed in 7 wt. % NaOH solution for 16 seconds. The wafers were rinsed in deionized water and dried by spinning. Pattern images have all the percentages of half-tones of the digital scale.

EXAMPLE 2

(5) A composition was made in the manner of Example 1 except that Eu naphthenate was changed with a mixture of Sm(NO.sub.3).sub.3 and Ce(NO.sub.3).sub.3. The hydrated lanthanide nitrates were prepared by dissolving the corresponding oxides in 50 wt. % nitric acid and evaporating the solution on a steam-bath. Sm(NO.sub.3).sub.3 and Ce(NO.sub.3).sub.3 represents each 1.5 wt. % of the composition. Exposure was decreased to 20 mJ/cm.sup.2. The procedure described in Example 1 remained unchanged. Inspection of the developed photoresist pattern confirmed a clear line/space pattern of 50 nm.

EXAMPLE 3

(6) One way to incorporate rare-earth ions into a photoresist is to encapsulate the ions in organic chelates and dope these complexes directly. The complex used in this example was Eu(fod).sub.3 or europium tris(6,6,7,7,8,8,8 heptafluoro-2,2dimethyl-3,5-octanedionate), purchased from Aldrich. One can accomplish doping of photoresist by simply dissolving the RE compound directly into the monomer. The photoresist was doped with 0.7 wt. % europium complex.

(7) Glycidyl methacrylate-allyl glycidyl ether copolymers are prepared by admixing the monomers in a solvent containing the polymerization catalyst after which the reaction mixture is heated to reflux. In a 3000 ml resin flask equipped with a reflux condenser, thermometer, stirrer assembly and addition funnel are placed 360 g of grycidyl methacrylate, 60 g allyl glycidyl ether, 750 ml of methyl ethyl ketone, 2.95 g Eu(fod).sub.3, and 0.982 g of benzoyl peroxide. The reaction solution is stirred while heating to reflux. Upon commencement of refluxing, a solution containing 2.97 g of benzoyl peroxide in 300 ml of methyl ethyl ketone is added slowly from the addition funnel over a period of about 90 minutes. The temperature of reflux is about 88 C. and is maintained, with stirring, over a total refluxing time of 5 hours after which the reaction mixture is permitted to cool to room temperature. Following cooling, 200 ml of additional methyl ethyl ketone is added with stirring after which the solution is filtered and added slowly, to 8 liters of methanol. The precipitated white product is collected and washed thoroughly with methanol after which is it suction dried at room temperature, obtaining 195 g of copolymers. The photoresist was obtained by mixing 5 g of glycidyl methacrylate-allyl glycidyl ether copolymers with 5 g o-chlorotolouene, 44.4 ml of butyronitrile and 0.25 g of 2,5-diethoxy-4-(p-tolylthio) benzene diazonium hexafluorophosphate. Exposure was established to 100 mJ/cm.sup.2. The procedure described in Example 1 remained unchanged. The development was carried out in an acetone methyl ethyl ketone solution. As a result, 80 nm lines and space patterns were formed with good shape.

(8) While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of the invention as described hereinabove and as defined by the appended claims.