Electron beam resist composition

• US 10,234,764 B2
• Filed: 07/30/2015
• Issued: 03/19/2019
• Est. Priority Date: 08/06/2014
• Status: Active Grant

• Current Assignee: University of Manchester
• Original Assignee: University of Manchester
• Inventors: Lewis, Scott, Winpenny, Richard, Yeates, Stephen
• Primary Examiner(s): Young, Christopher G
• Application Number:
  US15/501,417
• Publication Number:
  US 20170235227A1
• Time in Patent Office: 1,328 Days
• Field of Search: 430296, 430942
• CPC Class Codes: G03F 7/0047 characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
• CPC Class Codes: G03F 7/027 Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/039 Macromolecular compounds which are photodegradable, e.g. positive electron resists G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023
• CPC Class Codes: G03F 7/2059 using a scanning corpuscular radiation beam, e.g. an electron beam
• CPC Class Codes: H01J 37/3175 Projection methods, i.e. transfer substantially complete pattern to substrate

Abstract

The present invention relates to an electron beam (eBeam) resist composition, particularly an (eBeam) resist composition for use in the fabrication of integrated circuits. Such resist compositions include an anti-scattering compound which minimizes scattering and secondary electron generation, thus affording extremely high resolution lithography. Such high resolution lithography may be used directly upon silicon-based substrates to produce integrated circuits, or may alternatively be used to produce a lithographic mask (e.g. photomask) to facilitate high-resolution lithography.

Claims

1. A method of performing electron-beam lithography, the method comprising:

i) providing an (eBeam) resist-coated substrate or applying an (eBeam) resist coating to a substrate;

ii) exposing part(s) of the (eBeam) resist coating to (electron beam) radiation to provide an exposed (eBeam) resist coating;

iii) developing the exposed (eBeam) resist coating to generate an (eBeam) resist pattern layer, the (eBeam) resist pattern layer comprising;

developer-insoluble coating portions of the (eBeam) resist coating; and

an array of grooves extending through the (eBeam) resist pattern layer;

iv) optionally modifying the substrate, substrate surface, or part(s) thereof, underlying the (eBeam) resist pattern layer;

v) optionally removing the (eBeam) resist pattern layer to provide a modified substrate;

vi) optionally repeating, one or more times, step iv) and/or steps i)-v) (optionally with an alternative resist coating, such as a photoresist, instead of the eBeam resist coating; and

optionally using alternative radiation during exposure, such as visible or ultraviolet light, instead of electron beam radiation) upon the modified substrate;

wherein the eBeam resist-coated substrate is a substrate coated with an eBeam resist coating;

wherein the eBeam resist coating comprises an optionally dried and/or cured eBeam resist composition;

wherein the eBeam resist composition comprises an anti-scattering compound;

wherein the anti-scattering compound has a density less than or equal to 1.3 g/cm³ and a molecular weight greater than or equal to 2000 g/mol.

2. The method of claim 1, wherein the anti-scattering compound comprises a primary metal complex (PMC), wherein the primary metal complex is a polymetallic cage.

3. The method of claim 2, wherein the anti-scattering compound comprises a linker component associated with one or more primary metal complexes in a hybrid complex of Formula B:

(PMC)_p(LINK)_l

wherein;

PMC is a primary metal complex and p is a value between 1 and 30 and is the number of moles of PMC per mole of hybrid complex of Formula B; and

wherein LINK is a linker component and l is a value between 1 and 10 and is the number of moles of LINK per mole of hybrid complex of Formula B;

wherein optionally either or both of the primary metal complex(es) and/or linker component(s) within a hybrid complex are each independently associated with any of the counterions, and/or the counterions may be associated with the hybrid complex as a whole;

wherein the anti-scattering compound optionally comprises one or more counterions associated with the hybrid complex as part of a hybrid complex salt, wherein the hybrid complex salt is defined by Formula C;

(C¹_i1C²_i2 . . . C^c_ic)(PMC)_p(LINK)_l

wherein C¹ is a first counterion, C² is a second counterion, and C^c is a cth counterion, wherein i1, i2, and is are the respective number of moles of each of C¹, C², . . . , and C^c per mole of hybrid complex salt of Formula C.

4. The method of claim 2, wherein the primary metal complex is defined by Formula I or comprises units defined by Formula I:

[M¹_xM²_y . . . Mⁿ_zn(monoLIG¹)_m1(monoLIG²)_{m2 . . .} (monoLIG¹)_mq(biLIG¹)_b1(biLIG²)_{b2 . . .} (biLIG^r)_br(optLIG^s) (optLIG¹)_o1(optLIG²)_{o2 . . .} (optLIG^s)_os];

wherein;

M¹ is a first metal species and x is the number of moles of M¹ per mole of primary metal complex, wherein x is a number between 1 and 16;

M² is a second metal species and y is the number of moles of M² per mole of primary metal complex, wherein y is a number between 0 and 7;

Mⁿ is an nth metal species and zn is the number of moles of each Mⁿ per mole of primary metal complex, wherein zn is a number between 0 and 6;

suitably between 0 and 2;

suitably 0;

monoLIG¹ is a first monodentate ligand and m1 is the number of moles of monoLIG¹ per mole of primary metal complex, wherein m1 is a number between 0 and 20;

monoLIG² is a second monodentate ligand and m2 is the number of moles of monoLIG² per mole of primary metal complex, wherein m2 is a number between 0 and 10;

monoLIG⁴ is a qth monodentate ligand and mq is the number of moles of each monoLIG⁴ per mole of primary metal complex, wherein mq is a number between 0 and 2;

biLIG^r is a first bidentate ligand and b1 is the number of moles of biLIG^r per mole of primary metal complex, wherein b1 is a number between 1 and 20;

biLIG² is a second bidentate ligand and b2 is the number of moles of biLIG² per mole of primary metal complex, wherein b2 is a number between 0 and 16;

biLIG^r is a rth bidentate ligand and br is the number of moles of each additional biLIG^r per mole of primary metal complex, wherein br is a number between 0 and 2;

optLIG¹ is a first optional extra ligand and o1 is the number of moles of optLIG¹ per mole of primary metal complex, wherein o1 is a number between 0 and 4;

optLIG² is a second optional extra/terminal ligand and o2 is the number of moles of optLIG² per mole of primary metal complex, wherein o2 is a number between 0 and 3;

optLIG^s is a sth optional extra/terminal ligand and os is the number of moles of each additional optional optLIG^s per mole of primary metal complex;

wherein os is a number between 0 and 2.

5. The method of claim 4, wherein the sum of x and y is between 4 and 16.

6. The method of claim 4, wherein M¹ is a trivalent metal species.

7. The method of claim 4, wherein M² is a divalent metal species.

8. The method of claim 6, wherein M¹ is a trivalent metal species selected from the group including Cr^III, Fe^III, V^III, Ga^III, Al^III, or In^III.

9. The method of claim 7, wherein M² is a divalent metal species selected from the group including Ni^II, Co^II, Zn^II, Cd^II, Mn^II, Mg^II, Ca^II, Sr^II, Ba^II, Cu^II, or Fe^II.

10. The method of claim 4, wherein:

biLIG¹ is a carboxylate defined by the formula —

O₂CR_B1 (or R_B1CO₂⁻

), wherein R_B1 is a hydrocarbyl moiety selected from (1-12C)alkyl, (1-12C)alkenyl, (1-12C)alkynyl, (3-8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, or aryl(1-3C)alkyl;

biLIG² is a carboxylate defined by the formula —

O₂CR_B2 (or R_B2CO₂), wherein R_B2 is a group comprising a basic or chelating group, and is selected from optionally substituted heterocyclyl, heteroaryl, heterocyclyl(1-6C)alkyl, heteroaryl(1-6C)alkyl, or is selected from (1-12C)alkyl, (1-12C)alkenyl, (1-12C)alkynyl, -8C)cycloalkyl, (3-8C)cycloalkenyl, (1-3C)alkyl(3-8C)cycloalkyl, (1-3C)alkyl(3-8C)cycloalkenyl, aryl, (1-3C)alkylaryl, or aryl(1-3C)alkyl;

optLIG¹ is either a solvent molecule or a polydentate ligand having a denticity greater than or equal to 3.

11. The method of claim 10, wherein the primary metal complex is defined or comprises units defined by either:

by the Formula IIa;

[M¹_8-yM²_yF₈(O₂CR_B1)_16-b2(O₂CR_B2)_b2]

by the Formula IIb;

[CR₇NiF₈(O₂CR_B1)_16-b2(O₂CR_B2)_b2];

by the Formula IIc;

[Cr₇NiF₈(O₂CR_B1)₁₆];

by the Formula IId;

[Cr₈F₈(O₂CR_B1)_16-b2(O₂CR_B2)_b2];

by the Formula IIe;

[Cr₈F₈(O₂CR_B1)₁₆];

or

by the Formula III;

[M¹_8-yM²_yF₃(O₂CR_B1)₁₅(Gluc-NH—

R_O1)], wherein Gluc-NH—

R_O1 is N-(1-8C)alkyl-D-glucamine.

12. The method of claim 3, wherein the or each linker component (LINK) is independently selected from:

i) a single atom, molecule, ion, or complex containing a single co-ordinating moiety capable of accepting or donating two or more lone pairs of electrons;

ii) a single molecule, ion, or complex comprising two or more co-ordinating moieties, each co-ordinating moiety being capable of accepting or donating one or more lone pairs of electrons;

iii) a molecule, ion, or complex defined by Formula IV;

Q-[CORE]-[W]_w

wherein;

[CORE] is absent or is the core of the linker component and comprises one or optionally more than one core groups;

Q is a group directly attached to [CORE] or to one or more core group(s) thereof, wherein Q comprises a co-ordinating moiety;

each W is a group independently directly attached to [CORE] or to one or more core group(s) thereof, and optionally further attached to one or more other W groups or to Q, each of which W independently comprises a co-ordinating moiety;

wherein w is an integer greater than zero.

13. The method of claim 12, wherein the linker component is:

a) a single atom, molecule, ion, or complex containing a single co-ordinating moiety capable of donating two or more lone pairs of electrons, and the linker component(s) is or comprises a group selected from halide, oxo, oxide, hydroxide (OH⁻

), (1-6C)alkoxide, (2-6C)alkenyloxy, (2-6C)alkynyloxy, formyl, carboxy, (1-6C)alkoxycarbonyl, (2-6C)alkanoyl, (2-6C)alkanoyloxy, sulpho, sulphide, hydrogensulphide, (1-6C)alkylthio, (2-6C)alkenylthio, (2-6C)alkynylthio, thiocarbonyl, heterocyclyl containing at least one internal heteroatom selected from oxygen or sulphur, or (where appropriate) a deprotonated form or salt thereof;

wherein any CH, CH₂, or CH₃ is optionally substituted;

b) a single atom, molecule, ion, or complex containing a single co-ordinating moiety capable of accepting two or more lone pairs of electrons, and the linker component(s) is or comprises a group selected from a metal cation, a Lewis acidic metal compound, a Lewis acidic metal complex, and/or a metal compound or complex comprising a leaving group or substitutable ligand

c) a single molecule, ion, or complex comprising two or more co-ordinating moieties, each being capable of donating one or more lone pairs of electrons, and the linker component(s) is or comprises one or more groups selected from halide, amino, cyano, imino, enamino, (1-6C)alkylamino, di-[(1-6C)alkyl]amino, tri-[(1-6C)alkyl]amino, oxo, oxide, hydroxide (OH⁻

), (1-6C)alkoxide, (2-6C)alkenyloxy, (2-6C)alkynyloxy, formyl, carboxy, (1-6C)alkoxycarbonyl, (2-6C)alkanoyl, (2-6C)alkanoyloxy, sulpho, sulphide, hydrogensulphide, (1-6C)alkylthio, (2-6C)alkenylthio, (2-6C)alkynylthio, thiocarbonyl, heterocyclyl containing at least one internal heteroatom selected from nitrogen, oxygen or sulphur, heteroaryl containing at least one internal hetero atom selected from nitrogen, oxygen or sulphur, or (where appropriate) a deprotonated form or salt thereof;

wherein any CH, CH₂, or CH₃ is optionally substituted;

d) a single molecule, ion, or complex comprising two or more co-ordinating moieties, each being capable of accepting one or more lone pairs of electrons, and the linker component(s) is or comprises one or more groups selected from a metal cation, a Lewis acidic metal compound, a Lewis acidic metal complex, and/or a metal compound or complex comprising a leaving group or substitutable ligand;

or

e) a molecule, ion, or complex defined by Formula IV, and;

(I) the [CORE] comprises a single core group to which the Q group and the or each of the W group(s) are commonly attached, wherein the single core group is selected from;

i) a divalent or multivalent optionally substituted acyclic core group;

ii) a divalent or multivalent cyclic or polycyclic core group;

iii) a divalent or multivalent core group comprising at least one cyclic or polycyclic group linked to one or more acyclic moieties and/or cyclic or polycyclic moieties;

or

iv) a divalent or multivalent macrocyclic core group;

(II) the [CORE] comprises a plurality of core groups which are indirectly linked together to form the [CORE] via the Q group and/or one or more of the or each of the W group(s), wherein each of such core groups are independently selected from;

i) a single atom, molecule, ion, or complex containing a single co-ordinating moiety capable of donating two or more lone pairs of electrons; and

/or

ii) a single molecule, ion, or complex comprising two or more co-ordinating moieties each capable of independently donating an electron lone pair;

or

(III) the [CORE], comprises a plurality of core groups and is defined by;

14. The method of claim 1, wherein the substrate comprises or consists essentially of a substrate base material, wherein the substrate base material is a lithographic plate, a material for a lithographic mask, or an electronic component substrate.

15. The method of claim 14, wherein the substrate base material is a single monolithic silicon crystal.

16. The method as claimed in any preceding of claim 1, wherein the eBeam resist composition further comprises a secondary electron generator which is or comprises a compound having an effective atomic number (Z_eff) greater than or equal to 15, wherein:

Z_eff=Σ

α

_iZ_i

where Z_i is the atomic number of the ith element in the compound, and α

_i is the fraction of the sum total of the atomic numbers of all atoms in the compound (i.e. the total number of protons in the compound) constituted by said ith element.

18. A method of fabricating an integrated circuit die or an integrated circuit wafer comprising a plurality of integrated circuit dice, the or each die comprising a plurality of electronic components, wherein the method comprises performing electron-beam lithography of claim 1 by:

i) providing, as defined in claim 1, an (eBeam) resist-coated substrate or applying, as defined in claim 1, an (eBeam) resist coating to a substrate; and

ii) exposing, as defined in claim 1, part(s) of the (eBeam) resist coating to electron beam radiation to provide an exposed (eBeam) resist coating;

iii) developing, as defined in claim 1, the exposed (eBeam) resist coating to generate an (eBeam) resist pattern layer, the (eBeam) resist pattern layer comprising;

developer-insoluble coating portions of the (eBeam) resist coating (i.e. ridges); and

an array of grooves extending through the (eBeam) resist pattern layer;

iv) modifying, as defined in claim 1, the substrate, substrate surface, or part(s) thereof, underlying the (eBeam) resist pattern layer;

v) removing, as defined in claim 1, the (eBeam) resist pattern layer to provide a modified substrate;

vi) optionally repeating, as defined in claim 1, one or more times, step iv) and/or steps i)-v) upon the modified substrate, (using either an eBeam resist coating or an alternative resist coating, (e.g., a photoresist);

with either electron beam radiation or alternative radiation during exposure; and

thereafter

vii) conductively interconnecting the electronic components of the or each die with conductor(s), if not already performed during one or more substrate/substrate-surface modifying steps, to provide an integrated circuit with external contact terminals;

viii) optionally performing one or more further finishing steps;

ix) optionally separating an integrated circuit die from a wafer comprising a plurality of integrated circuit dice;

wherein the eBeam resist-coated substrate is a substrate coated with an eBeam resist coating;

wherein the eBeam resist coating comprises an optionally dried and/or cured resist composition;

wherein the eBeam resist composition comprises an anti-scattering as defined in a claim 1;

wherein the resist-coated substrate is a substrate coated with a resist coating, whether an eBeam resist coating as defined in claim 1 or an alternative resist coating (e.g., a photoresist);

wherein the resist coating comprises an optionally dried and/or cured resist composition, whether an eBeam resist composition as defined in claim 1 or an alternative resist composition (e.g., a photoresist).

19. A method of manufacturing an integrated circuit package, the integrated circuit package comprising a plurality of pins and an integrated circuit die with external contact terminals conductively connected to the corresponding plurality of pins, wherein the method comprises

providing an integrated circuit die by a method of fabricating an integrated circuit die of claim 18;

and thereafter;

i) attaching the integrated circuit die to a package substrate, wherein the package substrate comprises electrical contacts, each of the electrical contacts being optionally connected or connectable to a corresponding pin;

ii) conductively connecting each of the external contact terminals of the integrated circuit die to corresponding electrical contacts of the package substrate; and

iii) optionally, and if necessary, connecting the electrical contacts of the package substrate to corresponding pins;

iv) encapsulating the integrated circuit die.

20. A method of manufacturing a circuit board comprising an integrated circuit package comprising a plurality of pins, wherein the method comprises

providing an integrated circuit package by a method of manufacturing an integrated circuit package as claimed in claim 19;

and thereafter;

conductively connecting the integrated circuit package to a circuit board.

21. A method of manufacturing an electronic device or system, the electronic device or system comprising or being connectable to a power source and comprising a circuit board conductively connected to or connectable to a power source, wherein the method comprises

providing a circuit board by the method of manufacturing a circuit board as claimed in claim 20;

and thereafter;

incorporating the circuit board within the electronic device or system.

17. An eBeam resist composition comprising an anti-scattering compound;

wherein the anti-scattering compound has a density less than or equal to 1.3 g/cm³ and a molecular weight greater than or equal to 2000 g/mol.