CN108827902A - A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure - Google Patents

A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure Download PDF

Info

Publication number
CN108827902A
CN108827902A CN201810654069.4A CN201810654069A CN108827902A CN 108827902 A CN108827902 A CN 108827902A CN 201810654069 A CN201810654069 A CN 201810654069A CN 108827902 A CN108827902 A CN 108827902A
Authority
CN
China
Prior art keywords
nano
antenna structure
terahertz
substance
detection sensitivity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201810654069.4A
Other languages
Chinese (zh)
Other versions
CN108827902B (en
Inventor
秦坚源
韩宝娟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Jiliang University
Original Assignee
China Jiliang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Jiliang University filed Critical China Jiliang University
Priority to CN201810654069.4A priority Critical patent/CN108827902B/en
Publication of CN108827902A publication Critical patent/CN108827902A/en
Application granted granted Critical
Publication of CN108827902B publication Critical patent/CN108827902B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • G01N21/31Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
    • G01N21/35Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
    • G01N21/3581Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
    • 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
    • G01N21/59Transmissivity

Landscapes

  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Toxicology (AREA)
  • Investigating Or Analysing Materials By Optical Means (AREA)

Abstract

The Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure that the present invention relates to a kind of belongs to Terahertz detection applied technical field.A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure, this method comprises the following steps:Step a, designed for the nano-antenna structure of detection;Step b, substance to be detected load is tested on nano-antenna body structure surface and records Terahertz transmission spectrum of the substance to be detected on nano-antenna body structure surface;Step c, judge that target substance whether there is by the variation of the transmitance of Terahertz transmission spectrum before and after analysis load test substance.Compared with existing fingerprint detection method, the present invention is in nano-antenna structure slit 105The electric field strength of magnitude and all band high transmittance this two major features, are greatly improved detection sensitivity, realize the identification and measurement of nanometer scale thickness targets substance.

Description

A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure
Technical field
The Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure that the present invention relates to a kind of, belongs to terahertz Hereby detect applied technical field.
Background technique
Due to the collective vibration of most of biomolecule, intermolecular or intramolecular rotation generates resonance, absorbs Characteristic frequency is located at terahertz wave band, therefore can be realized the absorption spectrum " fingerprint " of THz wave to various by substance The category identification of substance, this is one of most attractive place in current Terahertz application.In addition, THz wave is with low Photon energy, weak radiation and it is transparent in most dielectric materials the features such as so that Terahertz in safety detection and Medical diagnosis on disease etc. has advantageous advantage.However, since most molecular structure sizes and absorption cross-section are compared to too Hertz wave (30-3000 μm) is very small, and the interaction strength of molecule and THz wave is very weak.In order to obtain apparent absorption Effect will often need the sample of larger volume or thicker size, traditional to be with transmission mode progress Terahertz fingerprint detection Substance to be detected is rolled into powder and is compressed into tablet form, (L.Ho, et are observed to it in conjunction with terahertz light spectrometer system al,Signatures and fingerprints,Nat.Photonics,Vol.2,no.9,pp.541-543,2008.).So And common thickness of sample is up to several millimeters under this mode, dosage is bigger, and which has limited THz wave fingerprint detections Application range.Researcher using a variety of methods be dedicated to improve the sensitivity of Terahertz fingerprint detection, such as increase electromagnetic wave with The interaction area of substance improves local electric field intensity etc..P.Weis(P.Weis,et al,Hybridization induced transparency in composites of metamaterials and atomic media, Opt.Express, Vol.19, no.23, pp.23573-23580,2011.) et al. propose between Meta Materials and detection molecules EIT effect detect target substance, although the structure is simple easy to process, the lactose of 50 μ m thicks its fingerprint signal is still Less than 10%, sensitivity is still not high enough;J.J.Yang(J.J.Yang,et al,Broadband molecular sensing with a tapered spoof plasmon waveguide,Opt.Express,Vol.23,no.7,pp.8583-8589, Et al. 2015.) using the interaction area that metallic tapered waveguides structure increases THz wave and detects substance to improve detection Sensitivity, but adjust its structural parameters be adapted to other substances detection when it is sufficiently complex;X Shi(X.Shi,et al, Enhanced terahertz fingerprint detection with ultrahigh sensitivity using the Cavity defect modes, Scientific Reports, Vol.7, no 1, pp 13147.) et al. utilize a kind of microcavity Mode of resonance improves detection sensitivity, although the detection of nanometer scale thickness targets substance may be implemented, to detection device Precise requirements are high, and operation difficulty is big, and analytic process is complicated.
Summary of the invention
Object of the present invention is to be directed to the prior art, there are the above problems, propose a kind of Terahertz based on nano-antenna structure Fingerprint detection sensitivity Enhancement Method, the technical problem to be solved is that the sensitivity for how improving Terahertz fingerprint detection for it.
The technical solution adopted by the present invention to solve the technical problems is:
A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure, this method include following step Suddenly:
Step a, designed for the nano-antenna structure of detection;
Step b, substance to be detected load is tested on nano-antenna body structure surface and records substance to be detected in nanometer Terahertz transmission spectrum on antenna structure surface;
Step c, target substance is judged by the variation of the transmitance of Terahertz transmission spectrum before and after analysis load test substance It whether there is.
The step of the method for the present invention is:Nano-antenna structure is that a transmissivity is very high approximate straight before loading substance Line, after loading substance, transmissivity reduces at the resonance frequency of load substance, to identify target substance, and by saturating The decline degree for penetrating rate to carry out quantitative analysis to target substance.The present invention is in nano-antenna structure slit 105Magnitude Detection sensitivity is greatly improved compared with previous fingerprint detection to the high sensitivity of target substance in electric field strength, realizes The identification and measurement of nanometer scale thickness targets substance, while can realize without changing structural parameters to plurality of target substance Detection, the high sensitivity detection suitable for mixed solution.
This method use in nano-antenna structure have high transmittance and resonance free feature, in conjunction with Terahertz through compose into Row analysis may be implemented the characteristic fingerprint detection of nanometer scale thickness mixed solution, have detection sensitivity high and fingerprint detection The features such as signal enhancing effect is obvious.
Preferably, the nano-antenna structure in the step a is the One Dimension Periodic narrow slit structure on metallic film. The metal can be any kind of metal.In terahertz wave band, any metal is all similar to perfect electric conductor.
Preferably, it is 10 that the narrow slit structure, which is length-width ratio,4The recessed grain of magnitude, the recess region is interior to be entered in Terahertz Have 10 when penetrating5The electric field strength of magnitude.Its slit areas is with the high feature of electric field strength, it can be achieved that the spy of nanometer scale thickness Levy fingerprint detection.Further preferably, the slit width d of the narrow slit structure is 100nm, and metal thickness t is 50nm, One Dimension Periodic It is 10 μm.The slit width of the narrow slit structure is smaller, and One Dimension Periodic is bigger, and metal thickness is bigger, and the electric field in groove is stronger.
Preferably, the antenna structure in the step a is placed on quartz substrate or silicon substrate.Substrate is to THz wave There is absorption, but plays a supportive role to antenna structure and be conducive to load detection substance.
Preferably, detecting first in the step b and recording nano-antenna structure before and after loading substance to be detected Terahertz transmission spectrum;Know in the step c by comparing the variation of nano-antenna structure transmission spectrum before and after load test substance The presence or absence of other target substance.
Preferably, in Terahertz transmission spectrum, transmissivity occurs at target substance resonance frequency in the step c When being decreased obviously, illustrate that target substance exists;When transmissivity is without being decreased obviously, illustrate that substance to be detected is not target substance.
Preferably, after judging that target substance exists in the step c, by calculating transmission spectrum in target substance resonance frequency Transmission slippage at rate calculates the loading capacity of target substance.It is related to the loading capacity of target substance to transmit slippage, this method Realizing the category identification of load substance simultaneously, moreover it is possible to realize to its quantitative analysis when load substance is consistent with target substance.
The beneficial effects of the invention are as follows:Compared with existing fingerprint detection method, the present invention is directed to nano-antenna structure slit Interior 105The electric field strength of magnitude and all band high transmittance this two major features, are greatly improved detection sensitivity, realize nanometer The identification and measurement of magnitude thickness targets substance, while inspection to plurality of target substance can be realized without changing structural parameters It surveys, the high sensitivity detection suitable for mixed solution.
Detailed description of the invention
Fig. 1 is nano-antenna structural schematic diagram, wherein PEC perfection electric conductor, t metal thickness, d slit width, E field Direction, H magnetic direction, the direction of k incidence THz wave;
A) nano-antenna structure itself Terahertz transmitance in Fig. 2;B) nano-antenna structure loads different-thickness on surface Transmitance when alpha-lactose;C) alpha-lactose of different-thickness itself transmitance;D) alpha-lactose of nano-antenna load different-thickness When with and without nano-antenna structure when through difference and the linear fit relationship of alpha-lactose thickness;
Fig. 3 is nano-antenna structure load resonance frequency respectively in the mixed solution of two kinds of substances of 0.529 and 0.7THz When transmitance.
Specific embodiment
Below by specific embodiment, and in conjunction with attached drawing, technical scheme of the present invention will be further explained in detail.It answers Work as understanding, implementation of the invention is not limited by the following examples, the accommodation in any form done to the present invention and/or Change falls within the scope of the present invention.
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc. It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field Rule method.
Embodiment:
A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure, specific step is as follows:
Step a, designed for the nano-antenna structure of detection;
Step b, substance to be detected load is tested on nano-antenna body structure surface and records substance to be detected in nanometer Terahertz transmission spectrum on antenna structure surface;
Step c, judge that target substance whether there is by analyzing the transmitance of Terahertz transmission spectrum.
The nano-antenna structure is the One Dimension Periodic narrow slit structure on metallic film.The narrow slit structure is length-width ratio It is 104The recessed grain of magnitude, the recess region is interior to have 10 in Terahertz incidence5The electric field strength of magnitude.Its slit areas tool There is the high feature of electric field strength, it can be achieved that the characteristic fingerprint of nanometer scale thickness detects.The metal can be any kind of Metal.In terahertz wave band, any metal is all similar to perfect electric conductor PEC.Antenna structure can be placed on quartz substrate Or on silicon substrate.Substrate has absorption to THz wave, but plays a supportive role to antenna structure and be conducive to load detectable substance Matter.
The structural schematic diagram of the nano-antenna structure is as shown in Figure 1:THz wave vertical incidence is formed in slit areas 105Order of magnitude high field.It in slit width d is 100nm by numerical computation method analog regulation structural parameters, metal is thick Degree t is 50nm, in the case where 10 μm of the period, from Fig. 2 (a) it can be seen that transmitance is greater than 90%, and approximate straight line.In nanometer After the alpha-lactose of the surface load different-thickness of antenna structure, transmitance figure such as Fig. 2 (b).Alpha-lactose is opposite in simulations Dielectric constant is characterized using Lorentz lorentz-harmonic oscillator (Lorentzian oscillators) model:
Wherein εIt is the background relative dielectric constant of off-resonance, ωpAnd γpBe respectively Intrinsic Gettering resonance angular frequency and Ratio of damping, Δ εpIt is the oscillation intensity factor.For simple computation, absorption of the alpha-lactose at 0.529THz is considered, only in order to more Experiment value others Lorentz lorentz's model parameter of coincideing well is:ε=3.145, γp=1.59*1011rad/s,Δεp=0.052 (A.Roggenbuck,et al,Coherent broadband continuous-wave terahertz spectroscopy on solid-state samples,New J.Phys.Vol.12,no.4,pp.043017,2010)。
Due to the high electric field strength of the nano-antenna structure slit areas, the absorption cross-section of alpha-lactose is greatly increased, from i.e. When alpha-lactose thickness being made to be only 150nm thickness, also presenting at 0.529THz through spectrum for total is decreased obviously, by original 96.95% come drops to 81.64%, changes 15.31%.From Fig. 2 (d) as can be seen that the load of nano-antenna structure is different Linear functional relation is presented in the alpha-lactose of thickness, transmitance difference and its thickness with and without structure.Transmitance difference is with its thickness The increase of degree and obviously increase.
In order to compare the detection effect of nano-antenna structure enhancing fingerprint, Fig. 2 (c) analog simulation α-of different-thickness The transmittance curve of lactose itself.From Fig. 2 (c), it can be seen that, transmitance of the alpha-lactose of 150nm at resonance frequency is decayed to Only 0.14%, even if increasing its thickness to 200nm even 250nm, also there was only 0.25% and 0.3% through decaying.And pass through It is loaded with the nano-antenna structure of 150nm thickness alpha-lactose, transmitance decays to 15.31%, than directly passing through 150nm thickness The transmitance change of alpha-lactose is exaggerated 109 times.
In order to verify this method to the evident characteristics of mixed solution, inventor exists lactose and another resonance frequency The mixed solution of the substance of 0.7THz is loaded in nano-antenna body structure surface.It is loaded with receiving with a thickness of the 150nm mixed solution The transmittance curve of rice antenna structure is as shown in Figure 3.As it can be seen that all going out at the resonance frequency 0.529 and 0.7THz of two kinds of solutes Now apparent transmitance changes.This further illustrates this method is applicable not only to single substance detection, same to mixed solution Effectively.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.

Claims (8)

1. a kind of Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure, it is characterised in that this method includes Following steps:
Step a, designed for the nano-antenna structure of detection;
Step b, substance to be detected load is tested on nano-antenna body structure surface and records substance to be detected in nano-antenna Terahertz transmission spectrum on body structure surface;
Step c, judge whether target substance is deposited by the transmitance variation of Terahertz transmission spectrum before and after analysis load test substance ?.
2. the Terahertz fingerprint detection sensitivity Enhancement Method according to claim 1 based on nano-antenna structure, special Sign is:Nano-antenna structure in the step a is the One Dimension Periodic narrow slit structure on metallic film.
3. the Terahertz fingerprint detection sensitivity Enhancement Method according to claim 2 based on nano-antenna structure, special Sign is:The narrow slit structure is that length-width ratio is 104The recessed grain of magnitude, the recess region is interior to have 10 in Terahertz incidence5 The electric field strength of magnitude.
4. the Terahertz fingerprint detection sensitivity Enhancement Method according to claim 3 based on nano-antenna structure, special Sign is:The slit width d of the narrow slit structure is 100 nm, and metal thickness t is 50 nm, and One Dimension Periodic is 10 μm.
5. the Terahertz fingerprint detection sensitivity Enhancement Method according to claim 1 based on nano-antenna structure, special Sign is:Antenna structure in the step a is placed on quartz substrate or silicon substrate.
6. the Terahertz fingerprint detection sensitivity Enhancement Method according to claim 1 based on nano-antenna structure, special Sign is:In the step b, detects first and record Terahertz transmission of the nano-antenna structure before and after loading substance to be detected Spectrum;Target substance is identified by comparing the variation of nano-antenna structure transmission spectrum before and after load test substance in the step c The presence or absence of.
7. the Terahertz fingerprint detection sensitivity Enhancement Method according to claim 6 based on nano-antenna structure, special Sign is:In the step c, in Terahertz transmission spectrum, when transmissivity is decreased obviously at target substance resonance frequency, Illustrate that target substance exists;When transmissivity is without being decreased obviously, illustrate that substance to be detected is not target substance.
8. the Terahertz fingerprint detection sensitivity Enhancement Method according to claim 7 based on nano-antenna structure, special Sign is:After judging that target substance exists in the step c, by calculating transmission of the transmission spectrum at target substance resonance frequency The loading capacity of slippage calculating target substance.
CN201810654069.4A 2018-06-22 2018-06-22 Terahertz fingerprint detection sensitivity enhancing method based on nano antenna structure Expired - Fee Related CN108827902B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810654069.4A CN108827902B (en) 2018-06-22 2018-06-22 Terahertz fingerprint detection sensitivity enhancing method based on nano antenna structure

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810654069.4A CN108827902B (en) 2018-06-22 2018-06-22 Terahertz fingerprint detection sensitivity enhancing method based on nano antenna structure

Publications (2)

Publication Number Publication Date
CN108827902A true CN108827902A (en) 2018-11-16
CN108827902B CN108827902B (en) 2021-02-26

Family

ID=64137896

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810654069.4A Expired - Fee Related CN108827902B (en) 2018-06-22 2018-06-22 Terahertz fingerprint detection sensitivity enhancing method based on nano antenna structure

Country Status (1)

Country Link
CN (1) CN108827902B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115046958A (en) * 2022-05-07 2022-09-13 中国计量大学 Terahertz super-surface enhanced fingerprint detection method based on incident angle scanning

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105590986A (en) * 2016-03-16 2016-05-18 侯皓文 Room temperature terahertz detector based on gallium nitride high electron mobility transistor and preparation method thereof
CN107064052A (en) * 2017-04-26 2017-08-18 中国计量大学 A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on microcavity mode of resonance

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105590986A (en) * 2016-03-16 2016-05-18 侯皓文 Room temperature terahertz detector based on gallium nitride high electron mobility transistor and preparation method thereof
CN107064052A (en) * 2017-04-26 2017-08-18 中国计量大学 A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on microcavity mode of resonance

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
孟阔: "太赫兹波段金属狭缝结构透射特性研究", 《中国优秀硕士学位论文全文数据库 基础科学辑》 *
肖健: "光电导天线产生太赫兹波的研究", 《中国优秀硕士学位论文全文数据库 基础科技辑》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115046958A (en) * 2022-05-07 2022-09-13 中国计量大学 Terahertz super-surface enhanced fingerprint detection method based on incident angle scanning

Also Published As

Publication number Publication date
CN108827902B (en) 2021-02-26

Similar Documents

Publication Publication Date Title
Seo et al. Terahertz biochemical molecule‐specific sensors
Peng et al. Terahertz spectroscopy in biomedical field: a review on signal-to-noise ratio improvement
Valensise et al. Removing non-resonant background from CARS spectra via deep learning
Manera et al. Magneto-Optical properties of noble-metal nanostructures: functional nanomaterials for bio sensing
Laserna Combining fingerprinting capability with trace analytical detection: surface-enhanced Raman spectrometry
CN107064052A (en) A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on microcavity mode of resonance
Chen et al. Rapid and sensitive biomarker detection using molecular imprinting polymer hydrogel and surface-enhanced Raman scattering
Xu et al. Rapid detection of sulfonamide antibiotics residues in swine urine by surface-enhanced Raman spectroscopy
Meng et al. Study on the enhancement mechanism of terahertz molecular fingerprint sensing
Wu et al. A review on current progress of Raman-based techniques in food safety: From normal Raman spectroscopy to SESORS
Al-Naib Evaluation of amplitude difference referencing technique with terahertz metasurfaces for sub-micron analytes sensing
CN108827902A (en) A kind of Terahertz fingerprint detection sensitivity Enhancement Method based on nano-antenna structure
Ji et al. A deep learning strategy for discrimination and detection of multi-sulfonamides residues in aquatic environments using gold nanoparticles-decorated violet phosphorene SERS substrates
Huang et al. Terahertz reconfigurable metasensor for specific recognition multiple and mixed chemical substances based on AIT fingerprint enhancement
Tomilin et al. Giant enhancement of the Faraday effect in a magnetoplasmonic nanocomposite
CN109187420A (en) Enhance the plate aerial detection device and its detection method of fingerprint detection sensitivity
CN115046958A (en) Terahertz super-surface enhanced fingerprint detection method based on incident angle scanning
CN108267429A (en) The quantitative analysis method of full iron and basicity in a kind of sinter
Schultz Demystifying SERS: a newcomer’s guide to using surface enhanced Raman scattering
Lu et al. Enhanced sensitivity of dilute aqueous adrenaline solution with an asymmetric hexagonal ring structure in the terahertz frequencies
Jie et al. Non-destructive detection of adulteration of weight-loss drugs in the field of spectral feature fusion
Wei et al. Machine-learning-assisted SERS nanosensor platform toward chemical fingerprinting of Baijiu flavors
Mandal et al. Vibrational line shape effects in plasmon-enhanced stimulated Raman spectroscopies
Hinrichs et al. Field manipulation of infrared absorption properties in thin films
Wang et al. A review of terahertz metamaterial sensors and their applications

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20210226

CF01 Termination of patent right due to non-payment of annual fee