CN109373916A - It is a kind of to realize the real time monitoring apparatus grown to Au film with TFBG - Google Patents

It is a kind of to realize the real time monitoring apparatus grown to Au film with TFBG Download PDF

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Publication number
CN109373916A
CN109373916A CN201811451508.8A CN201811451508A CN109373916A CN 109373916 A CN109373916 A CN 109373916A CN 201811451508 A CN201811451508 A CN 201811451508A CN 109373916 A CN109373916 A CN 109373916A
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China
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tfbg
film
time monitoring
real time
polarization
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CN201811451508.8A
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Chinese (zh)
Inventor
沈常宇
张崇
宫佳琦
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China Jiliang University
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China Jiliang University
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Priority to CN201811451508.8A priority Critical patent/CN109373916A/en
Publication of CN109373916A publication Critical patent/CN109373916A/en
Priority to CH000985/2019A priority patent/CH715639B9/en
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01JMEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
    • G01J3/00Spectrometry; Spectrophotometry; Monochromators; Measuring colours
    • G01J3/28Investigating the spectrum
    • G01J3/42Absorption spectrometry; Double beam spectrometry; Flicker spectrometry; Reflection spectrometry
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01BMEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00Measuring arrangements characterised by the use of optical techniques
    • G01B11/02Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
    • G01B11/06Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
    • G01B11/0616Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating
    • G01B11/0683Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating measurement during deposition or removal of the layer
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1675Process conditions
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/42Coating with noble metals
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01BMEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
    • G01B11/00Measuring arrangements characterised by the use of optical techniques
    • G01B11/02Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness
    • G01B11/06Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material
    • G01B11/0616Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating
    • G01B11/0625Measuring arrangements characterised by the use of optical techniques for measuring length, width or thickness for measuring thickness ; e.g. of sheet material of coating with measurement of absorption or reflection
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55Specular reflectivity
    • G01N21/552Attenuated total reflection
    • G01N21/553Attenuated total reflection and using surface plasmons
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/7703Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides
    • G01N21/774Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator using reagent-clad optical fibres or optical waveguides the reagent being on a grating or periodic structure
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/0004Gaseous mixtures, e.g. polluted air
    • G01N33/0009General constructional details of gas analysers, e.g. portable test equipment
    • G01N33/0027General constructional details of gas analysers, e.g. portable test equipment concerning the detector
    • G01N33/0036Specially adapted to detect a particular component
    • G01N33/005Specially adapted to detect a particular component for H2
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/25Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
    • G01N2021/258Surface plasmon spectroscopy, e.g. micro- or nanoparticles in suspension

Abstract

The invention discloses a kind of real time monitoring apparatus realized with TFBG and grown to Au film, by amplified spontaneous emission source, polarizing film, Polarization Controller, TFBG, temperature controller, spectrometer composition.After the surface TFBG deposits Au film, spectral characteristic will receive influence.Due to the surface plasma resonance effect of Au film and medium interface, after through TFBG, larger difference is will be present in transmission spectrum for two polarised light S light and P light in cross polarization.The Polarization Dependent Loss variation of TFBG in Au thin-film process is plated to realize the controllable deposition to Au film by real-time monitoring, and the real time monitoring to the Au film thickness of growth can be realized.

Description

It is a kind of to realize the real time monitoring apparatus grown to Au film with TFBG
Technical field
The invention belongs to metal nanometer thin film preparation technical fields, and in particular to a kind of realized with TFBG grows Au film Real time monitoring device.
Background technique
Hydrogen is also important the raw material of industry as the highly important clean energy resource of today's society, and various necks are widely applied Domain.But since hydrogen is colourless odorless, it is easy to which the diffusion leakage from medium encounters open fire and easily explodes, so research is used It is very necessary in the hydrogen gas sensor of detection and monitoring.Previous Optical Fider Hybrogen Sensor is although sensitivity is very high, design It is more difficult, therefore metal coating Optical Fider Hybrogen Sensor is studied, it has many advantages, such as small in size, high sensitivity. Wherein noble metal plays key effect in this sensor as hydrogen sensitive material.Metal nano is prepared using chemical reduction method Particle, and enable its be attached to above substrate formed nano thin-film can be with the performance of Optimization of Hydrogen sensor.
In the growth course of metal nanometer thin film, underlayer temperature, growth time, each growth parameter(s) pair such as external environment The product weight of the single-item film eventually formed all has a significant impact.In previous test, generally complete by hand all Technological operation, not only test mission is heavy, and manual operations inevitably bring human error, have studied one kind thus The method of feasible real-time monitoring Au film growth, is become by the Polarization Dependent Loss that real-time monitoring plates TFBG in Au thin-film process Change to realize the controllable deposition to Au film, convenient for the thickness of the metal nanometer thin film of regulation preparation, to effectively increase plating Film quality.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of real time monitoring dresses realized with TFBG and grown to Au film It sets, which may be implemented the Polarization Dependent Loss variation of TFBG during real-time monitoring plating Au nano thin-film, and then realization pair The controllable deposition of Au film obtains high-test metal nano thin-film to be applied in hydrogen gas sensor.Because it is simple with equipment, The advantages that at low cost, regulates and controls the physical characteristics such as the thickness of metal nanometer thin film in which can be convenient.Therefore before tool deposits very big development Scape and research significance.
The invention is realized by the following technical scheme: it is a kind of to realize the real time monitoring apparatus grown to Au film with TFBG, By amplified spontaneous emission source (1), polarizing film (2), Polarization Controller (3), TFBG (4), temperature controller (5), work pool (6), work Make liquid (7), spectrometer (8) composition;It is characterized by: the light of amplified spontaneous emission source (1) outgoing is incident by polarizing film (2) To in Polarization Controller (3), the right end of Polarization Controller (3) is connected with TFBG (4), and TFBG (4) is placed in work pool (6), And heated using temperature controller (5), TFBG (4) right end is connected with spectrometer (8);By the spectroscopic data measured and use atomic force microscopy The result that mirror AFM demarcates film thickness is associated, and the monitoring to growing film thickness can be realized.
TFBG (4) is pre-processed first before plated film, is cleaned by ultrasonic 5 points with organic solvent ethyl alcohol, acetone and methanol respectively Clock, with dense H2SO4And H2O2Volume ratio is that 7:3 solution handles 15 minutes at 80 DEG C, hydroxylated TFBG (4) are immersed 1% It APTMS methanol solution 0.5 hour, is adsorbed for Au nanoparticle.
Temperature controller (5) the control temperature is held constant at 22.5 DEG C.
The working solution (7) is the mixed solution of concentration 0.01% gold chloride and 0.4 mM of hydroxylamine hydrochloride.
The working principle of the invention is: after the surface TFBG deposits Au film, will affect its spectral characteristic.Due to Au film With the SPR effect of medium interface, after through TFBG, transmission spectrum will appear larger the polarised light s light and p light of two cross polarizations Difference.This characteristic can be described with Polarization Dependent Loss (PDL).PDL is defined as:
Wherein TxAnd TyIt is the transmitted spectrum of s and p-polarization state.Based on the above basic principle, can with the structure of design come pair Spectrum real-time monitoring in the growth course of film.By the spectroscopic data measured and the result phase demarcated with AFM to film thickness Association, can be realized the monitoring to growing film thickness.In addition, usually sensed with the SPR characteristic of Au film modified TFBG, It is best that this requires the SPR of film to match, and frosting phenomenon is most obvious.Therefore, it even if changing reaction condition, can also be surveyed in real time To spectrum in observe maximum SPR frosting phenomenon when, at once stop plated film.
Detailed description of the invention
Fig. 1 is a kind of real time monitoring apparatus schematic diagram realized with TFBG and grown to Au film.
Specific embodiment
TFBG (4) is pre-processed first before plated film, is cleaned by ultrasonic 5 points with organic solvent ethyl alcohol, acetone and methanol respectively Clock, and with ultrapure water rinsing drying, with dense H2SO4And H2O2Volume ratio is that 7:3 solution handles 15 minutes, by hydroxyl at 80 DEG C The TFBG (4) of change immerses APTMS methanol solution 0.5 hour of 1%, adsorbs for Au nanoparticle;In coating process, in room temperature It is lower that TFBG (4) is placed in deposition life in the hybrid working liquid (7) that concentration is 0.01% gold chloride and 0.4 mM of hydroxylamine hydrochloride Long Au nano thin-film, and so that temperature is held constant at 22.5 DEG C using temperature controller (5).
As shown in Figure 1, a kind of realize the real time monitoring apparatus grown to Au film with TFBG, by amplified spontaneous emission source (1), polarizing film (2), Polarization Controller (3), TFBG (4), temperature controller (5), work pool (6), working solution (7), spectrometer (8) group At;It is characterized by: the light of amplified spontaneous emission source (1) outgoing is incident in Polarization Controller (3) by polarizing film (2), The right end of Polarization Controller (3) is connected with TFBG (4), and TFBG (4) is placed in work pool (6), and is added using temperature controller (5) Heat, TFBG (4) right end are connected with spectrometer (8), start timing and real-time monitoring spectrum.Solution temperature is 22.5 in coating process It DEG C keeps constant.
First 5 minutes for can measuring in plated film are tested, there are lesser recess at 1530nm-1540nm;30 minutes when Time start to appear apparent recess at 1540nm, at 1540nm Polarization Dependent Loss amplitude with the growth of sedimentation time it is continuous Reduce, and drift about to long wave length direction, when the time of plated film proceeding to 50 minutes, the maximum recess of Polarization Dependent Loss expands It opens up near 1542nm.
Final step, washes with water the TFBG for having plated film and use is dried with nitrogen.The TFBG that Au nano thin-film is wrapped up points Not Jin Ru water, in dehydrated alcohol and be exposed in air.According to the experimental results, in air, TFBG is not occurred bright Aobvious SPR phenomenon;When TFBG immerses ultrapure water, occurs maximum SPR resonance frosting phenomenon at 1543nm;It is molten in dehydrated alcohol In liquid, SPR resonant wavelength is near 1565nm, but delustring is not most obviously, to illustrate that SPR wavelength at this time is not best match Value.

Claims (1)

1. a kind of realize the real time monitoring apparatus grown to Au film with TFBG, by amplified spontaneous emission source (1), polarizing film (2), Polarization Controller (3), TFBG(4), temperature controller (5), work pool (6), working solution (7), spectrometer (8) composition;Its feature Be: the light of amplified spontaneous emission source (1) outgoing is incident in Polarization Controller (3) by polarizing film (2), Polarization Controller (3) right end is connected with TFBG(4), and TFBG(4) is placed in work pool (6), and is heated using temperature controller (5), TFBG(4) it is right End is connected with spectrometer (8);First to TFBG(4 before plated film) it pre-processes, it is super with organic solvent ethyl alcohol, acetone and methanol respectively Sound cleans 5 minutes, with dense H2SO4And H2O2Volume ratio is that 7:3 solution handles 15 minutes, by hydroxylated TFBG(4) at 80 DEG C APTMS methanol solution 0.5 hour of 1% is immersed, is adsorbed for Au nanoparticle;In coating process, TFBG(4) is placed in concentration For deposition growing Au nano thin-film in the hybrid working liquid (7) of 0.01% gold chloride and 0.4 mM of hydroxylamine hydrochloride, and utilize Temperature controller (5) makes temperature be held constant at 22.5 DEG C.
CN201811451508.8A 2018-11-30 2018-11-30 It is a kind of to realize the real time monitoring apparatus grown to Au film with TFBG Pending CN109373916A (en)

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CN201811451508.8A CN109373916A (en) 2018-11-30 2018-11-30 It is a kind of to realize the real time monitoring apparatus grown to Au film with TFBG
CH000985/2019A CH715639B9 (en) 2018-11-30 2019-08-05 Apparatus for real-time monitoring of the growth of an Au thin film by TFBG.

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Citations (5)

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CN101718571A (en) * 2009-12-04 2010-06-02 天津理工大学 Tilt fiber bragg grating (TFBG) liquid level change measuring instrument
CN103604777A (en) * 2013-12-02 2014-02-26 暨南大学 Orthogonal polarization optical fiber biological refractive index sensor and detecting method thereof
US20150140556A1 (en) * 2012-06-20 2015-05-21 Spartan Bioscience Inc. Optical fiber with grating and particulate coating
CN105887052A (en) * 2016-05-04 2016-08-24 中国计量大学 Side surface coating method and device for oblique fiber Bragg grating
CN107741409A (en) * 2017-09-15 2018-02-27 武汉理工大学 A kind of cancer markers detection means and method based on slant Bragg grating

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101718571A (en) * 2009-12-04 2010-06-02 天津理工大学 Tilt fiber bragg grating (TFBG) liquid level change measuring instrument
US20150140556A1 (en) * 2012-06-20 2015-05-21 Spartan Bioscience Inc. Optical fiber with grating and particulate coating
CN103604777A (en) * 2013-12-02 2014-02-26 暨南大学 Orthogonal polarization optical fiber biological refractive index sensor and detecting method thereof
CN105887052A (en) * 2016-05-04 2016-08-24 中国计量大学 Side surface coating method and device for oblique fiber Bragg grating
CN107741409A (en) * 2017-09-15 2018-02-27 武汉理工大学 A kind of cancer markers detection means and method based on slant Bragg grating

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
冯建松: "基于Pd/Au纳米粒子的光纤表面等离子体共振氢气传感器研究", 《中国优秀硕士学位论文全文数据库信息科技辑》 *
杨蕊竹等: "长周期光纤光栅的特性及传感应用的研究", 《中国博士学位论文全文数据库信息科技辑》 *

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CH715639B9 (en) 2023-07-14
CH715639B1 (en) 2023-05-31

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