SiGe Etching Composition for Selective Removal Over Germanium

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Solution Overview

Problem

Conventional aqueous etching solutions for silicon-germanium alloy films in semiconductor manufacturing lack selectivity and compatibility with nitride/oxide masks, leading to inefficient removal of sacrificial SiGe layers and surface roughness issues during the fabrication of Ge nanowire channels in GAA MOSFETs.

Innovation Solution

An aqueous etching solution comprising a quinone oxidizer, fluoride ion source, water-miscible solvent, corrosion inhibitor, and surfactant, which provides enhanced selectivity and compatibility, allowing for the selective removal of silicon-germanium over germanium with controlled etch rates and surface quality.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If conventional aqueous etching solutions (HF/H2O2/CH3COOH) are used for SiGe etching, then etch selectivity towards SiGe over Si is improved, but compatibility with nitride/oxide masks deteriorates due to high etch rate on oxide and nitride

Engineering Contradiction:
Improveetch selectivityVSAvoidmask damage
Core Design Contradiction:
Manufacturing precisionVSObject-affected harmful factors

Solution Approach 1:

The patent changes the chemical parameters of the etching solution by replacing the conventional HF/H2O2/CH3COOH chemistry with a novel composition containing ammonium bifluoride, hydrobromic acid, and hydrogen peroxide. This parameter change achieves both high SiGe etch selectivity (greater than 2:1 over Ge) and compatibility with nitride/oxide masks by controlling the etch rates of all materials involved

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses a composite etching solution formulation combining multiple chemical components (ammonium bifluoride, hydrobromic acid, hydrogen peroxide, and water) that work synergistically. This composite chemistry provides selective SiGe removal while protecting masks, resolving the contradiction between selectivity and mask compatibility

Inventive Principle:
Principle #40Composite materials

2Ease of manufacture

If conventional etching solutions are used for SiGe removal, then etching process is simplified, but surface roughness increases leading to poor nanowire quality

Engineering Contradiction:
Improveetching process simplicityVSAvoidsurface roughness
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The patent modifies the chemical composition parameters to include specific concentrations of ammonium bifluoride (0.1-10 wt%), hydrobromic acid (1-50 wt%), and hydrogen peroxide (0.1-10 wt%). These parameter adjustments enable the etching process to maintain simplicity while producing smooth surfaces with minimal roughness, ensuring high nanowire quality

Inventive Principle:
Principle #35Parameter changes

3Productivity

If high etch rate chemistry is used for rapid SiGe removal, then productivity increases, but selectivity control deteriorates making it difficult to prevent substrate trench recession

Engineering Contradiction:
Improveetch rateVSAvoidselectivity control
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The patent optimizes the concentration parameters of the etching components to achieve the right balance: ammonium bifluoride (0.1-10 wt%) provides etching power while hydrobromic acid (1-50 wt%) and hydrogen peroxide (0.1-10 wt%) enhance selectivity. This parameter optimization enables both high productivity through rapid SiGe removal and precise selectivity control to prevent unwanted substrate trench recession

Inventive Principle:
Principle #35Parameter changes

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 solution achieves selective etching of silicon-germanium with a selectivity greater than 2, compatibility with nitride/oxide masks, and prevents surface roughness, ensuring successful fabrication of Ge nanowire channels with minimal chemical contamination.

Implementation Method 1

The composition comprises: water; oxidizer; water-miscible organic solvent; fluoride ion source

Methodology Applied
Scientific EffectOxidation: Oxidation

Implementation Method 2

A H2O2/CH3COOH/HF mixture is highly selective towards Si1-xGex over Si

Methodology Applied
Scientific EffectChemical etching: Chemical Bonding

Implementation Method 3

The composition may also comprise at least one surfactant

Methodology Applied
Scientific EffectSurfactant action: Surfactant

Implementation Method 4

The composition may also comprise at least one corrosion inhibitor

Methodology Applied
Scientific EffectCorrosion inhibition: Adsorption

Data Source

PatentEP3537473B1Etching solution for selectively removing silicon-germanium alloy from a silicon-germanium/ germanium stack during manufacture of a semiconductor device
Publication Date: 2024.05.01 VERSUM MATERIALS US LLC
  • EP3537473B1 patent drawingFigure 1A~1B

AI summary

Described herein is an etching solution comprising water; an oxidizer; a water-miscible organic solvent; a fluoride ion source; a corrosion inhibitor and optionally, a surfactant, optionally a buffer, optionally a chelating agent. Such compositions are useful for the selective removal of silicon-germanium over germanium from a microelectronic device having such material(s) thereon during its manufacture.