Stressed Titania Film Bandgap Shift via Acid Etching

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Solution Overview

Problem

Current methods for producing titania electrodes are inefficient in creating photoactive surfaces with shifted bandgaps, limiting their effectiveness in photo-induced reactions such as hydrogen production from water.

Innovation Solution

A process involving acid etching of titanium metal to form nano-structured surfaces, followed by anodizing or heat oxidation to create stressed titania films with a lower bandgap, utilizing impure titanium grades like Grade 1 or Grade 2, and controlling stress through substrate undulations to achieve enhanced photocatalytic activity.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional methods are used to produce titania electrodes, then the manufacturing process is simpler, but the photocatalytic efficiency and bandgap shift are insufficient

Engineering Contradiction:
Improvephotocatalytic efficiencyVSAvoidmanufacturing process complexity
Core Design Contradiction:
ReliabilityVSDevice complexity

Solution Approach 1:

The patent applies preliminary action by first acid-etching the titanium substrate to create nanostructures before forming the titania layer. This pre-prepared nanostructured surface then guides the subsequent anodizing or oxidation process to produce the desired stressed titania film with improved photocatalytic properties

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent changes physical parameters by controlling the acid etching conditions (concentration, temperature, time) and oxidation parameters (anodizing voltage, heating temperature) to achieve specific nanostructure geometries and stress states in the titania film, thereby optimizing the bandgap shift and photocatalytic efficiency

Inventive Principle:
Principle #35Parameter changes

2Reliability

If high purity titanium is used, then the material quality is better, but the cost and manufacturing complexity increase

Engineering Contradiction:
Improveelectrode performanceVSAvoidmanufacturing cost
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent changes the material parameter by using commercially pure titanium (99.6-99.7% purity) instead of high purity titanium, and compensates for the lower purity by optimizing the acid etching and oxidation process parameters to achieve the desired nanostructure quality and photocatalytic performance

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses cheaper commercially pure titanium that can be readily obtained, accepting that it requires more aggressive acid etching to achieve the desired nanostructure, but this approach significantly reduces material cost while still achieving functional equivalence through process optimization

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

3Ease of manufacture

If the titania film is made thin, then the manufacturing is easier, but the photocatalytic activity is reduced

Engineering Contradiction:
Improvefilm formation easeVSAvoidphotocatalytic activity
Core Design Contradiction:
Ease of manufactureVSReliability

Solution Approach 1:

The patent creates a porous nanostructured titania film through acid etching followed by anodizing or oxidation. The porous structure increases the effective surface area and active sites for photocatalysis, allowing thinner films to achieve higher photocatalytic activity than conventional dense films of the same thickness

Inventive Principle:
Principle #31Porous materials

Solution Approach 2:

The patent transitions from a two-dimensional dense film to a three-dimensional porous nanostructure. The vertical nanotubes or nanorods provide increased surface area and light scattering, enhancing photocatalytic activity while maintaining thin overall film thickness for ease of manufacture

Inventive Principle:
Principle #17Another dimension (Dimensionality change)

4Productivity

If the bandgap is not shifted, then the titania is more stable, but the solar energy conversion efficiency is limited

Engineering Contradiction:
Improvesolar energy conversion efficiencyVSAvoidtitania stability
Core Design Contradiction:
ProductivityVSStability of the object's composition

Solution Approach 1:

The patent changes the stress parameter in the titania film by creating tensile stress through the acid etching and anodizing process. This stress induces a bandgap shift that extends light absorption into the visible range, improving solar energy conversion efficiency while maintaining the anatase crystal structure stability

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite structure combining the titanium substrate with the stressed titania overlayer. The underlying titanium provides structural stability while the stressed titania layer provides enhanced photocatalytic function with shifted bandgap, achieving both stability and improved solar energy conversion

Inventive Principle:
Principle #40Composite materials

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 process results in titania electrodes with improved photocatalytic efficiency, capable of efficiently producing hydrogen from water using solar radiation, with increased bandgap shift and reduced energy requirements, suitable for large-scale, cost-effective solar energy conversion applications.

Implementation Method 1

subjecting titanium metal to an acid etchant; step (a) forms a titanium nano-structured surface on the titanium metal

Methodology Applied
Scientific EffectChemical etching: Erosion

Implementation Method 2

anodizing the titanium in an anodizing solution

Methodology Applied
Scientific EffectAnodizing: Anodising

Implementation Method 3

heating the titanium in an oxygen-containing atmosphere

Methodology Applied
Scientific EffectThermal oxidation: Oxidation

Implementation Method 4

the titania film produced in step (b) is stressed by the nanostructures, the stress causing the titania film to have a lower bandgap than unstressed titania

Methodology Applied
Scientific EffectStress-induced bandgap shift:

Implementation Method 5

capable of efficiently producing hydrogen from water using solar radiation

Methodology Applied
Scientific EffectPhotoexcitation: Photoelectric Effect

Data Source

PatentEP2289108B1Bandgap-shifted semiconductor surface and apparatus
Publication Date: 2017.05.10 NANOPTEK CORP
  • EP2289108B1 patent drawingFigure 1
  • EP2289108B1 patent drawingFigure 2A
  • EP2289108B1 patent drawingFigure 2B

AI summary

Titania is a semiconductor and photocatalyst that is also chemically inert. With its bandgap of 3.2 and greater, to activate the photocatalytic property of titania requires light of about 390 nm wavelength, which is in the ultra-violet, where sunlight is very low in intensity. A method and devices are disclosed wherein stress is induced and managed in a thin film of titania in order to shift and lower the bandgap energy into the longer wavelengths that are more abundant in sunlight. Applications of this stress-induced bandgap- shifted titania photocatalytic surface include photoelectrolysis for production of hydrogen gas from water, photovoltaics for production of electricity, and photocatalysis for detoxification and disinfection.