Electron beam resist composition

• US 10,613,441 B2
• Filed: 11/20/2018
• Issued: 04/07/2020
• 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:
  US16/197,133
• Publication Number:
  US 20190324370A1
• Time in Patent Office: 504 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 minimises 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. An antiscattering resist composition for fabricating an integrated circuit die or an integrated circuit wafer, the composition comprising an anti-scattering compound, wherein the antiscattering compound is a polymetallic metal-organic complex comprising a primary metal complex (PMC).

2. The antiscattering resist composition of claim 1, further comprising a scattering compound comprising one or more electron-containing π

- and/or p-orbitals, suitably characterized by alkene and/or alkyne moieties, optionally wherein the scattering compound comprises one or more atoms capable of datively co-ordinating with the anti-scattering compound/complex.

3. The antiscattering resist composition of claim 1, further comprising a secondary electron generator, which secondary electron generator is or comprises a compound comprising a d-block, p-block, or f-block metal species having an atomic number greater than or equal to 49;

wherein;

optionally the secondary electron generator 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;

optionally the antiscattering compound/complex forms one or more dative bonds with the secondary electron generator.

4. The antiscattering resist composition of claim 1, wherein the antiscattering compound is heterometallic.

5. The antiscattering resist composition of claim 4, wherein at least one metal species of the antiscattering compound is a transition metal species.

6. The antiscattering resist composition of claim 1, wherein the antiscattering compound comprises:

at least one trivalent metal species selected from the group consisting of Cr^III, Fe^III, V^III, Ga^III, Al^III, and In^III, most suitably Cr^III; and

at least one divalent metal species selected from the group consisting of Ni^II, Co^II, Zn^II, Cd^II, Mn^II, Mg^II, Ca^II, Sr^II, Ba^II, Cu^II, and Fe^II, most suitably Ni^II.

7. The antiscattering resist composition of claim 1, wherein the anti-scattering compound has a solubility of at least 10 mg/g in hexane.

8. The antiscattering resist composition of claim 1, wherein the antiscattering compound comprises a ligand which is a linker component that is capable of acting as a lewis acid and/or a lewis base.

9. The antiscattering resist composition of claim 1, wherein the antiscattering compound itself serves as a resist component, whose developer-solubility properties change following exposure to radiation.

10. The antiscattering resist composition of claim 1, wherein the composition comprises 20-99 wt % solvent.

11. The antiscattering resist composition of claim 1, wherein the composition is a solution.

12. The antiscattering resist composition of claim 11, wherein the composition is free of any dispersed or suspended particulate matter.

13. The antiscattering resist composition of claim 1, wherein the composition is spin-coatable.

14. The antiscattering resist composition of claim 1, wherein the anti-scattering compound controls the flow and/or scattering of electrons when exposed to radiation.

15. The antiscattering resist composition of claim 1, wherein the anti-scattering compound has a density less than or equal to 1.5 g/cm³.

16. 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:

i) providing an antiscattering resist-coated substrate or applying an antiscattering resist coating to a substrate; and

ii) exposing parts of the resist coating to radiation to provide an exposed resist coating;

OR

i) providing;

a. a resist-coated substrate or applying a resist coating to a substrate; and

b. a lithographic mask comprising a mask pattern characterised by regions of surface/substrate transparency juxtaposed with regions of surface/substrate opacity, wherein the lithographic mask is obtained by performing lithography upon an anti scattering resist-coated mask substrate; and

ii) exposing parts of the resist coating, through the lithographic mask to radiation to provide an exposed resist coating;

AND THEN

iii) developing the exposed resist coating to generate a resist pattern layer, the resist pattern layer comprising;

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

an array of grooves extending through the resist pattern layer;

iv) modifying the substrate, substrate surface, or parts thereof, underlying the resist pattern layer;

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

vi) optionally repeating, one or more times, upon the modified substrate step iv) and/or steps i)-v) with either an antiscattering resist coating or an alternative resist coating, optionally using alternative radiation;

vii) conductively interconnecting the electronic components of the or each die with conductors 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 antiscattering resist-coated substrate is a substrate coated with an antiscattering resist coating;

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

the antiscattering resist composition is as claimed in claim 1.

17. 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:

i) providing an integrated circuit die by or obtained by a method of fabricating an integrated circuit die as claimed in claim 16;

ii) 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;

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

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

v) encapsulating the integrated circuit die.

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

i) providing an integrated circuit package by or obtained by a method of manufacturing an integrated circuit package as claimed in claim 17;

ii) conductively connecting the integrated circuit package to a circuit board.

19. 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:

i) providing a circuit board by or obtained by the method of manufacturing a circuit board as claimed in claim 18;

ii) incorporating the circuit board within the electronic device or system.

20. The method of fabricating an integrated circuit die or an integrated circuit wafer of claim 16, wherein the radiation used during exposure of the antiscattering resist coating is ionizing radiation.

21. The method of claim 16, wherein the average thickness of the antiscattering resist coating is 10-200 nm.