CN108254591A - The full optical magnetic field sensors of diamond nano, probe and atomic force microscope - Google Patents

The full optical magnetic field sensors of diamond nano, probe and atomic force microscope Download PDF

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Publication number
CN108254591A
CN108254591A CN201711381052.8A CN201711381052A CN108254591A CN 108254591 A CN108254591 A CN 108254591A CN 201711381052 A CN201711381052 A CN 201711381052A CN 108254591 A CN108254591 A CN 108254591A
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magnetic field
diamond
fluorescence lifetime
nano
detection device
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CN201711381052.8A
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Inventor
孙方稳
陈向东
李燊
赵博文
郭光灿
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University of Science and Technology of China USTC
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University of Science and Technology of China USTC
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q60/00Particular types of SPM [Scanning Probe Microscopy] or microscopes; Essential components thereof
    • G01Q60/24AFM [Atomic Force Microscopy] or apparatus therefor, e.g. AFM probes
    • G01Q60/26Friction force microscopy
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q70/00General aspects of SPM probes, their manufacture or their related instrumentation, insofar as they are not specially adapted to a single SPM technique covered by group G01Q60/00
    • G01Q70/08Probe characteristics
    • G01Q70/10Shape or taper
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01QSCANNING-PROBE TECHNIQUES OR APPARATUS; APPLICATIONS OF SCANNING-PROBE TECHNIQUES, e.g. SCANNING PROBE MICROSCOPY [SPM]
    • G01Q70/00General aspects of SPM probes, their manufacture or their related instrumentation, insofar as they are not specially adapted to a single SPM technique covered by group G01Q60/00
    • G01Q70/08Probe characteristics
    • G01Q70/14Particular materials

Abstract

The present invention relates to a kind of full optical magnetic field sensors of diamond nano, probe and atomic force microscope.Wherein, the full optical magnetic field sensors of diamond nano include:Diamond nano structure containing nitrogen vacancy colour center is configured to change fluorescence lifetime and photoluminescence intensity under different magnetic field;Luminescence generated by light detects device and/or fluorescence lifetime detection device, and the luminescence generated by light detection device is configured to detect the fluorescence lifetime, and fluorescence lifetime detection device is configured to detect the photoluminescence intensity.

Description

The full optical magnetic field sensors of diamond nano, probe and atomic force microscope
Technical field
The invention belongs to nanosensor fields, are mainly used in full optical magnetic field and measure, and are suitble to electromagnetic environment complicated, high electric The particular surroundings induced fields such as pressure measurement etc., is specifically related to the full optical magnetic field sensors of diamond nano, further relates to wrap The probe of the diamond nano structure of nitrogenous-vacancy colour center, is further directed to the atomic force microscope containing above-mentioned probe.
Background technology
Nano-sensor is that either sensitivity reaches nanoscale or sensor and substance to be detected or object to shape size The interaction distance between body is nano level.The sensor made using nanometer technology, size reduces, precision improves, property It can substantially improve, nano-sensor is to stand on an atomic scale, so as to be greatly enriched the theory of sensor, has pushed sensing The production technique of device has widened the application field of sensor.Nano-sensor is in biology, chemistry, machinery, aviation, military affairs The fields of grade obtain extensive development.
Current Nano diamond magnetic field nanometer imaging technique, main utilize are attached to atomic force microscope (AFM) probe On nitrogenous-vacancy colour center (NV) Nano diamond particle, using optical reading electronic self-rotary resonant technology (ODMR), come pair Determinand carries out the high-accuracy magnetic field imaging of nanoscale.And in ODMR technologies, important condition is to need to introduce microwave to grasp Make the electron spin in NV.However the introducing of this condition, lead to not realize complete optical magnetic field sensing technology.
Invention content
(1) technical problems to be solved
In view of this, the purpose of the present invention is to provide a kind of full optical magnetic field sensors of diamond nano, probe and originals Sub- force microscope, at least partly to solve the problems, such as techniques discussed above.
(2) technical solution
According to an aspect of the present invention, provide a kind of diamond nano full optical magnetic field sensors, including:
Diamond nano structure containing nitrogen-vacancy colour center is configured to change fluorescence lifetime and light under different magnetic field Photoluminescence intensity;
Luminescence generated by light detects device and/or fluorescence lifetime detection device, and the luminescence generated by light detection device is configured to detect The fluorescence lifetime, fluorescence lifetime detection device are configured to detect the photoluminescence intensity.
In a further embodiment, the luminescence generated by light detection device includes avalanche diode, single photon counter With high-speed figure capture card;The fluorescence lifetime detection device includes avalanche diode, single photon counter, pulse signal and occurs Device and high-speed figure capture card.
In a further embodiment, the diamond nano structural material containing nitrogen-vacancy colour center is nanometer Grain or nano wire.
In a further embodiment, the diamond nano structure setting containing nitrogen-vacancy colour center is in a Buddha's warrior attendant On ground mass bottom, the diamond substrate is monocrystalline or polycrystalline material.
In a further embodiment, single nitrogen-sky is contained in the diamond nano structure containing nitrogen-vacancy colour center Position colour center or multiple nitrogen-vacancy colour center of array arrangement.
According to another aspect of the invention, a kind of diamond nano probe containing nitrogen-vacancy colour center is provided, including:
Diamond nano structure containing nitrogen-vacancy colour center is configured to change fluorescence lifetime and light under different magnetic field Photoluminescence intensity.
In a further embodiment, the Nano diamond of single nitrogenous-vacancy colour center is installed in the probe;Or Probe described in person contains the Nano diamond of multiple nitrogenous-vacancy colour centers, and the Nano diamond of multiple nitrogenous-vacancy colour centers is in Array is arranged.
In a further embodiment, the probe has a diamond substrate, the diamond containing nitrogen-vacancy colour center Nanostructured is set in the substrate.
In accordance with a further aspect of the present invention, a kind of atomic force microscope is provided, including:
A kind of probe of any of the above is configured to remain unchanged in the illumination of reception and during changes of magnetic field close to magnetic field Fluorescence lifetime and photoluminescence intensity generate variation;
Luminescence generated by light detects device and/or fluorescence lifetime detection device, and the luminescence generated by light detection device is configured to detect The fluorescence lifetime, fluorescence lifetime detection device are configured to detect the photoluminescence intensity.
In a further embodiment, the luminescence generated by light detection device includes avalanche diode, single photon counter With high-speed figure capture card;The fluorescence lifetime detection device includes avalanche diode, single photon counter, pulse signal and occurs Device and high-speed figure capture card
Compared to traditional Nano diamond magnetic field sensing technology, this utilization diamond NV defects that the present invention is shown exist Luminescence generated by light in magnetic field changes and the method for sensing of service life change obviously can radiate to avoid external microwave is introduced and relevant Microwave device enormously simplifies equipment group and is filled with and relevant device cost;
Further it can realize that equipment micromation and core devices are integrated, such as will contain using the technology of the present invention Diamond nano structure and luminescence generated by light the detection device and fluorescence lifetime detection device of nitrogen-vacancy colour center integrate, and are optical fiber Full optical magnetic field sensors have established technical foundation.
Description of the drawings
Fig. 1 is that level systems of the physical principle NV of the embodiment of the present invention in the presence of no external magnetic field B manipulates mould with microwave Type schematic diagram;
Fig. 2A and Fig. 2 B are the physical principle NV of the embodiment of the present invention respectively without and with seven energy in the presence of external magnetic field B Grade system contrast model schematic diagram;
Fig. 3 is the important physical conclusion schematic diagram of the embodiment of the present invention, partly shows that the service life of NV increases with magnetic field on Fig. 3 And reduce, Fig. 3 lower parts show that photoluminescence intensity increases with magnetic field and reduced;
Fig. 4 is the micro-nano technology technique signal of the diamond nano line probe array containing single NV of the embodiment of the present invention Figure;
Fig. 5 is the scanning electron microscope (SEM) photograph in kind processed according to Fig. 4 techniques;
Fig. 6 is a kind of probe-type application apparatus figure of the embodiment of the present invention;
Fig. 7 a are the fluorescent intensity of the embodiment of the present invention and the schematic diagram of magnetic field dependence;Fig. 7 b are the glimmering of the embodiment of the present invention Light service life and the schematic diagram of magnetic field dependence.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with specific embodiment, and reference Attached drawing, the present invention is described in further detail.Advantages of the present invention and effect will pass through content disclosed in this invention It is and more notable.Illustrate that appended attached drawing simplified and used as illustrating herein.Attached component count shown in figure, shape and ruler It is very little to modify according to actual conditions, and the configuration of component is likely more complexity.Also other aspects can be carried out in the present invention Practice or application, and without departing from spirit and scope defined in the present invention under conditions of, various change and adjustment can be carried out.
According to existing Nano diamond magnetic field sensing technology, need to be introduced into microwave to operate the electron spin in NV, so And the introducing of this condition, lead to not realize complete optical magnetic field sensing technology.
The basic conception of the present invention is, utilizes nano fluorescent structure --- the NV colour centers in diamond realize full optics magnetic Field sensing and method, using full optical magnetic field measuring technique, eliminate some device architecture complexities, can be external to avoid introducing Microwave radiation and relevant microwave device.
One side according to embodiments of the present invention provides a kind of diamond nano full optical magnetic field sensors, including:
Diamond nano structure containing nitrogen-vacancy colour center is configured to change fluorescence lifetime and light under different magnetic field Photoluminescence intensity;
Luminescence generated by light detects device and/or fluorescence lifetime detection device, and the luminescence generated by light detection device is configured to detect The fluorescence lifetime, fluorescence lifetime detection device are configured to detect the photoluminescence intensity.
In some embodiments, the luminescence generated by light detection device includes avalanche diode, single photon counter and high speed Data Acquisition Card.
In some embodiments, the fluorescence lifetime detection device packet includes avalanche diode, single photon counter, pulse Signal generator and high-speed figure capture card.
The material that the embodiment of the present invention can be applied to has:Diamond nano structural material containing NV (receive by nano particle Rice noodles etc.) and diamond single crystal containing NV or polycrystalline bulk material and they various tied substantially containing diamond NV colour centers The derivative of structure or micro-nano technology structure.
The embodiment of the present invention utilizes following principle:
I) nitrogen negatively charged in diamond-vacancy colour center (NV) defect be by with the sky in diamond adjacent cells position The associated nitrogen-atoms (N) that substitutes in position (V) forms, and has C3v symmetrical structures, symmetry axis is in nitrogen-atoms --- on the line of vacancy, Its Vacancy captures electronics.Under outer magnetic field condition, the photoinduction spin polarization of this NV defects and spin correlation luminescence generated by light (PL) it can become inefficient, the information in the magnetic field about this can be extracted using NV defects optic response.Again because of NV colour centers Lattice structure minimum dimension~0.5nm, it is possible to for nanosensor field.
By taking single NV as an example, such as Fig. 1, using the millisecond pulse light of 532m by NV colour centers, spin polarization in bulk diamond To the excitation state of ms=0, then apply the pulse of microwave half period;Excitation state is made to be turned to ms=± 1 by ms=0, then again into Row fluorescence lifetime measurement.The service life of excitation state ms=0 repeatedly measured is 12.0ns, and the service life of excitation state ms=± 1 is 7.8ns, aging variation is mainly since ms=± 1 is caused by metastable nonradiative transition process.
As shown in Figure 2 A and 2 B, NV models are thought of as seven level systems.Because of each energy level (comprising splitting energy level and Intermediate state energy level) the life time of the level and fluorescent emission intensity difference.It is constant in conditions such as external laser, only change the feelings in magnetic field Under condition, external magnetic field can cause NV electron energy level cloth inning to change (laser reduces the polarization of NV electron spins), The relaxation time of its fine-structure levels changes, and fluorescence lifetime is caused to reduce, and photoluminescence intensity increases with magnetic field and reduced.
Ii) interpretation of quantum mechanics of above-mentioned reason is as follows:
Consider that there are NV during outfield-Ground state Hamiltonian is written as:
It can see NV-Energy level it is affected by magnetic fields larger, without influence of the equidirectional magnetic field to energy level also not Equally.Under normal conditions in diamond stress influence very little, here we ignored.Consider that spin for 1 system, solves Xue Determine straightforward words equationIt obtains:
It willβ is abbreviated as, and is enabledEnergy eigenvalues equation is then obtained (after for simplicity, Face will use natural unit system, i.e.,):
Solution formula (1.3) can obtain ground state level distribution.But generally for simplicity, perturbation approximation may be used to locate in we Reason.Because null field splitting D corresponds to magnetic field of the 1000 Gauss sizes along the symmetrical axis directions of NV, thus can be by the magnetic field of tens Gausses It influences to consider into perturbation (geμB|B|D).In this way:
Matrix form be:
Zero level intrinsic energy is:
The single order of energy is modified toSecond order is modified toTherefore it adds in Behind magnetic field, the correction term of energy is:
It can be seen that, in low-intensity magnetic field, vertical direction magnetic field is to the contribution of energy shift than axis from formula (1.9) Contribution to magnetic field is small.There are external magnetic field in an axial direction, two energy level m of script degeneracys=± 1 produces and splits It splits.Simultaneously because perpendicular to axial magnetic field, ms=± 1 and msEnergy level spacing between=0 is widened.
The Hamiltonian variation of NV ground state levels (Spin-triplet) caused by the symmetrical axis direction magnetic fields of NV only has diagonal item, The eigenstate of spin will not be changed;And there is nondiagonal term in the magnetic field Hamiltonian of symmetrical axis direction.Work as vertical direction When magnetic field is very strong, the eigenstate of system is no longer spin ms=0, ± 1, but their superposition state.Laser is to spin in this way Polarization will reduce.
So NV colour center cloth inning change overall trend is caused by the enhancing of external magnetic field:Service life is smaller and luminescence generated by light The small corresponding energy level of intensity cloth inning distribution increase, as a result be exactly experiment measure the single NV colour centers service life with magnetic field increase and Reduce, photoluminescence intensity increases with magnetic field and reduced, as shown in figs. 7 a and 7b.
According to above analysis, the physical principle of the embodiment of the present invention and conclusion of the present invention are as shown in figure 3, when external magnetic field (B) In the range of 0-150G, single NV luminescence generated by lights (PL) STATISTICAL STRENGTH value in diamond nano structure with magnetic field (B) increasing Reduce greatly, and contrast declines generally more than 30%;Its fluorescence lifetime statistical value also reduces with the increase in magnetic field.It can Know, the service life that NV is partly described on Fig. 3 increases with magnetic field and reduced, and Fig. 3 lower parts have demonstrated photoluminescence intensity with magnetic field Increase and reduce.
The embodiment of the present invention also provides a kind of diamond nano probe containing single NV, is used as full optical magnetic field and visits Survey sensor.A kind of micro-nano technology process schematic representation such as Fig. 4 of typical diamond nano probe array, step are as follows:
First, spin coating HSQ is 300nm again after deposition 300nm thickness SiNx on the diamond (referring to subgraph (a));
Then through the following steps:Developing fixing (referring to subgraph (b)) after electron beam exposure, disk size are diameter 200nm;Reactive ion etching SiNx (referring to subgraph (c));Inductively ion etching diamond forms height 1.6um's Probe array (referring to subgraph (d));N~+ implantation (referring to subgraph (e));NV is generated after high vacuum annealing (referring to subgraph (f))。
The scanning electron microscope (SEM) photograph in kind processed according to Fig. 4 techniques as shown in figure 5, and it includes be single NV verification and Fluorescence lifetime detects as shown in figs. 7 a and 7b.
Another aspect according to embodiments of the present invention provides a kind of nanometer Buddha's warrior attendant of atomic force microscope operation colour center containing NV The method that stone measures magnetic field, including:
Diamond nano structure containing nitrogen-vacancy colour center is configured to change fluorescence lifetime and light under different magnetic field Photoluminescence intensity.
In some instances, the Nano diamond of single nitrogenous-vacancy colour center is installed in probe;Or the probe contains There is the Nano diamond of multiple nitrogenous-vacancy colour centers, and the Nano diamond of multiple nitrogenous-vacancy colour centers is arranged in array.
In some embodiments, probe has a diamond substrate, and the diamond nano structure containing nitrogen-vacancy colour center is set It puts in the substrate.
It is according to embodiments of the present invention in another aspect, provide a kind of atomic force microscope, including:
Above-described probe is configured to remain unchanged in the illumination of reception and when changes of magnetic field is glimmering close to magnetic field Light service life and photoluminescence intensity generate variation;
Luminescence generated by light detects device and/or fluorescence lifetime detection device, and the luminescence generated by light detection device is configured to detect The fluorescence lifetime, fluorescence lifetime detection device are configured to detect the photoluminescence intensity.
Here luminescence generated by light detection device includes avalanche diode, single photon counter and high-speed figure capture card;Institute It states fluorescence lifetime detection device and includes avalanche diode, single photon counter, pulse signal generator and high-speed figure capture card.
As shown in fig. 6, the Nano diamond that the colour center containing NV is operated for atomic force microscope measures a kind of specific reality in magnetic field Apply mode, i.e., it is single in Nano diamond particle (or the AFM entirety probe processed with bulk diamond) on afm tip NV colour centers read Magnetic Field with optical method.Measurement process is:Probe 501 is with the Nano diamond of colour center containing NV on needle point Particle is moved near the magnetic field of the transmitting of magnetic field generator 502, movable mirror 505 and coaxial digital CCD camera lens 506 with And under speculum 504 assists, object lens 503 are focused on Nano diamond particle;Then movable mirror 505 is removed.Swash Optical diode 507 is mapped to through the transmitting 532nm illumination of too short pass filter piece 508 on the Nano diamond of probe 501, NV colors therein The heart, which is excited, emits the fluorescence of 637nm or so, and by single photon counter 509, (luminescence generated by light detects device after fluorescence is filtered And/or one kind of fluorescence lifetime detection device) collect, by the signal processing to single photon counter 509, obtain fluorescent intensity According to luminescence generated by light and fluorescence lifetime, point by point scanning sample surfaces are simultaneously imaged, and can reflect sample for information and fluorescence lifetime information The changes of magnetic field of surface nanoscale grade.
Choose data that NV colour center measures as shown in figs. 7 a and 7b, therefore the fluorescent intensity observed in an experiment It can be influenced with fluorescence lifetime by the size and Orientation in magnetic field, the service life of NV increases with magnetic field and reduced, photoluminescence intensity Increase with magnetic field and reduce.
The embodiment of the present invention passes through research and utilization nano fluorescent structure --- and the NV colour centers in diamond realize full optics magnetic Field sensing and method avoid realization nanometer magnetic field sensing under the conditions of the introducing of external microwave radiation;It is surveyed using full optical magnetic field Amount technology eliminates some device architecture complexities, simple and reliable for structure, using convenient, measurement fast response time, magnetic field intensity Wide range of measurement.
Particular embodiments described above has carried out the purpose of the present invention, technical solution and advantageous effect further in detail Describe in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the protection of the present invention Within the scope of.

Claims (10)

1. a kind of full optical magnetic field sensors of diamond nano, it is characterised in that including:
Diamond nano structure containing nitrogen-vacancy colour center is configured to change fluorescence lifetime and photic hair under different magnetic field Luminous intensity;
Luminescence generated by light detects device and/or fluorescence lifetime detection device, and the luminescence generated by light detection device is configured to described in detection Fluorescence lifetime, fluorescence lifetime detection device are configured to detect the photoluminescence intensity.
2. the full optical magnetic field sensors of diamond nano according to claim 1, which is characterized in that the luminescence generated by light inspection It surveys device and includes avalanche diode, single photon counter and high-speed figure capture card;The fluorescence lifetime detection device includes snow Collapse diode, single photon counter, pulse signal generator and high-speed figure capture card.
3. the full optical magnetic field sensors of diamond nano according to claim 1, which is characterized in that described to contain nitrogen-sky The diamond nano structural material of position colour center is nano particle or nano wire.
4. the full optical magnetic field sensors of diamond nano according to claim 1, which is characterized in that described to contain nitrogen-sky For the diamond nano structure setting of position colour center in a diamond substrate, the diamond substrate is monocrystalline or polycrystalline material.
5. the full optical magnetic field sensors of diamond nano according to claim 1, which is characterized in that described to contain nitrogen-sky Multiple nitrogen-vacancy the colour center arranged in the diamond nano structure of position colour center containing single nitrogen-vacancy colour center or array.
6. a kind of diamond nano probe containing nitrogen-vacancy colour center, it is characterised in that including:
Diamond nano structure containing nitrogen-vacancy colour center is configured to change fluorescence lifetime and photic hair under different magnetic field Luminous intensity.
7. probe according to claim 6, which is characterized in that single nitrogenous-vacancy colour center is equipped in the probe Nano diamond;Or the probe contains the Nano diamond of multiple nitrogenous-vacancy colour centers, and multiple nitrogenous-vacancy colour centers Nano diamond in array arrange.
8. probe according to claim 6, which is characterized in that the probe has a diamond substrate, contains nitrogen-vacancy In the diamond nano structure setting of the colour center substrate.
9. a kind of atomic force microscope, it is characterised in that including:
Any probes of claim 6-8 are configured to remain unchanged in the illumination of reception close to magnetic field and magnetic field becomes Fluorescence lifetime and photoluminescence intensity generate variation during change;
Luminescence generated by light detects device and/or fluorescence lifetime detection device, and the luminescence generated by light detection device is configured to described in detection Fluorescence lifetime, fluorescence lifetime detection device are configured to detect the photoluminescence intensity.
10. atomic force microscope according to claim 9, which is characterized in that the luminescence generated by light detection device includes snow Collapse diode, single photon counter and high-speed figure capture card;The fluorescence lifetime detection device includes avalanche diode, monochromatic light Sub-count device, pulse signal generator and high-speed figure capture card.
CN201711381052.8A 2017-12-19 2017-12-19 The full optical magnetic field sensors of diamond nano, probe and atomic force microscope Pending CN108254591A (en)

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CN109342548A (en) * 2018-11-26 2019-02-15 中国科学技术大学 The measurement method and system of carrier concentration
CN113678041A (en) * 2019-01-30 2021-11-19 华威大学 Defect center based sensor
WO2020239172A1 (en) * 2019-05-25 2020-12-03 Bernd Burchard Device and method for using diamond nanocrystals having nv colour centres in cmos circuits
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WO2022116521A1 (en) * 2020-12-04 2022-06-09 国仪量子(合肥)技术有限公司 Quantum diamond precision magnetic measurement system based on single spin
CN113514786A (en) * 2021-04-15 2021-10-19 中国科学技术大学 Integrated sensor based on solid state spinning in diamond
CN117705831A (en) * 2024-02-05 2024-03-15 高速铁路建造技术国家工程研究中心 Quantum sensor based on microwave reflection and nondestructive detection method
CN117705831B (en) * 2024-02-05 2024-04-26 高速铁路建造技术国家工程研究中心 Quantum sensor based on microwave reflection and nondestructive detection method

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