Zirconium Spin-On Formulations for Stable Etch-Resistant ZrOx Films
Find Innovative SolutionsGenerate Solutions
Solution Overview
Problem
Conventional metal oxide compositions used in semiconductor manufacturing are unstable in air due to moisture, leading to shelf-life stability issues and performance shortcomings, and there is a need for stable, soluble metal oxides suitable for spin-on hard masks and antireflective underlayers with high etch resistance.
Innovation Solution
A newly identified polymorph of zirconium (IV) propionate (ZPPA) is synthesized by reacting zirconium(IV)(tert-butoxide)4 with propionic anhydride and propionic acid, and then with propylene glycol monomethyl ether, forming stable formulations that include additives for managing film properties, which are used to create highly crosslinked ZrOx films with enhanced etch resistance and low Argon sputtering rates.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Reliability
If conventional metal oxide compositions are used in spin-on formulations, then etch resistance can be achieved, but shelf-life stability deteriorates due to moisture instability in air
Solution Approach 1:
The patent uses organic precursors (zirconium alkoxides, zirconium carboxylates) as intermediary compounds that are stable in air and can be spin-coated. These precursors decompose during thermal processing to form the desired metal oxide hard mask, thereby mediating between the need for air stability and the need for etch-resistant oxide films.
Solution Approach 2:
The patent changes the chemical state of the metal oxide from fully oxidized (unstable) to precursor forms (stable). By controlling the oxidation state and molecular structure of the precursor compounds, the formulation achieves both air stability and subsequent etch resistance after thermal decomposition and oxide formation.
2Reliability
If high concentrations of metal oxide are present in the underlayer, then etch resistance and thermal conductance are improved, but formulation stability deteriorates due to moisture sensitivity
Solution Approach 1:
Organic precursors serve as stable intermediaries that can be formulated at high concentrations without moisture sensitivity. These precursors maintain formulation stability during storage and application, then convert to high-concentration metal oxide films during thermal processing, achieving both formulation stability and high etch resistance.
Solution Approach 2:
The patent creates composite spin-on formulations containing organic precursors, solvents, and additives. This composite structure allows high metal content to be delivered in a stable, processable form that maintains formulation integrity while enabling high etch resistance in the final oxide film.
3Ease of manufacture
If spin coating is used to deposit hard masks, then manufacturing complexity and cost are reduced, but material stability deteriorates due to moisture instability of metal oxide compositions
Solution Approach 1:
The patent introduces organic precursor compounds as intermediaries that are compatible with spin-coating processes. These precursors are stable in air, allowing simple spin-on application without special atmosphere control, then convert to etch-resistant oxides during thermal processing, thereby enabling ease of manufacture while maintaining material stability.
4Reliability
If conventional hard masks with high etch resistance are used, then pattern transfer capability is improved, but application complexity increases due to requirement for vapor deposition techniques
Solution Approach 1:
The patent replaces complex vapor deposition systems with simple spin-coating equipment. By formulating metal oxide precursors in solution form, the invention substitutes sophisticated physical vapor deposition machinery with conventional liquid coating equipment, thereby reducing application complexity while maintaining pattern transfer capability through the etch-resistant oxide film.
Applied Scientific Principles
This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.
Function Achieved in This Case
The ZPPA formulations produce robust ZrOx films with etch resistivity greater than 0.1 Å/sec and Ar sputtering rates lower than 20 Å/sec, effectively filling lithographic features and forming patterned films on substrates with low void formation.
Implementation Method 1
A newly identified polymorph of zirconium (IV) propionate (ZPPA) is synthesized by reacting zirconium(IV)(tert-butoxide)4 with propionic anhydride and propionic acid
Implementation Method 2
spin-on metal-organic formulations have been developed to replace CVD/PVD/ALD hard masks
Implementation Method 3
formulations include ZPP and/or ZPPA and methods of making and using the formulations to make highly crosslinked ZrOx films
Data Source
AI summary
The disclosed and claimed subject matter relates to spin-on metal-organic formulations that include zirconium.