CN109705857A

CN109705857A - Diamond nano needle construction and the preparation method and application thereof

Info

Publication number: CN109705857A
Application number: CN201711018185.9A
Authority: CN
Inventors: 杨扬; 唐永炳; 张文军
Original assignee: Shenzhen Institute of Advanced Technology of CAS
Current assignee: Shenzhen Institute of Advanced Technology of CAS
Priority date: 2017-10-25
Filing date: 2017-10-25
Publication date: 2019-05-03
Anticipated expiration: 2037-10-25
Also published as: CN109705857B

Abstract

A kind of several diamond nano needles that diamond nano needle construction includes diamond body layer and extends in the diamond body layer surface, the adjacent diamond nano needle are spaced each other, and colour center structure is also distributed in diamond nano needle surface layer.A kind of diamond nano needle construction preparation method, which includes the steps that etching diamond film layer, to be formed diamond nano needle, grow delta- doped layer in diamond nano wire surface and carry out electron beam irradiation and annealing to delta- doped layer.A kind of diamond nano needle construction is used to prepare the device to Intracellular delivery substance.

Description

Diamond nano needle construction and the preparation method and application thereof

Technical field

The invention belongs to technical field of biological materials, a kind of diamond nano needle construction and its preparation side are related particularly to Method and application.

Background technique

Diamond is based on the fluorescence of excellent physics, chemical property and biocompatibility and Nano diamond spy Property and surface group modifiability, and then make nanostructured diamond material biomedicine field application obtain extensively Concern.As a kind of excellent biocompatible materials, colour center such as nitrogen-vacancy (NV) in diamond are by replacing in diamond The composite construction of the carbon vacancy (V) at position nitrogen-atoms (N) and ortho position composition, shows the photostability and thermal stability of superelevation, Fluorescence is not influenced by size, surface modification.However, NV colour center is to the physical quantitys quite sensitive such as magnetic field, temperature, stress, electric field, And there is the long relevant and relaxation time at room temperature, therefore be commonly used for the high-sensitivity measurement of these physical indexs.It is based on The above advantage, diamond NV nano material become the ideal of the fluorescent marker of cell, three-dimensional tracking, bio-imaging and bio-sensing Fluorescence probe.However, the preparation of high quality NV colour center exists only in diamond nano-particles and high quality single crystal diamond chip, Greatly limit their application range.

In addition to the diamond particles of nano-scale, the diamond nano needle array of nearest vertical arrangement is applied to efficiently Intracellular transmission and detection.This target is realized relative to the method for chemistry and biology, and diamond nano needle is in cell delivery In show apparent advantage, have the characteristics that general, easy to operate, efficient, cost is relatively low and safe, can be controllable general Transmission of materials is to intracellular certain organs.Using height it is vertical wide than nano material machinery pierce through cell membrane be increasingly becoming it is a kind of great The means of prospect detected into the cell to Intracellular delivery substance and realization.Some researches show that can use silicon nanowires or silicon Nano needle arrays realize the application of intracellular neural network detection and Intracellular drug transmission.Compared with silicon nano material, Buddha's warrior attendant Stone nanowire structure can still keep very high Young's modulus, yield strength and breaking strength.It discloses at present a kind of using golden Hard rock nano needle arrays simply and easily can be transmitted directly using this method to the device of intracellular delivery substance and need to enter The biomolecule of cell penetrates cell membrane.Chemotherapeutics, antibody and other biological molecule can be transferred directly to cytoplasm It is interior, without transmitting signal path by traditional cell.Using this method can Successful transfection nerve cell, transfection efficiency Up to 45%, it is only necessary to when 10 minutes, and at present commercial method transfection generally below 5%, take a few hours.In another document Also disclose the nanometer using materials such as diamond, cubic boron nitride, carbonitride, boron nitride, boron-doping carbonitride, metal borides Same purpose may be implemented in needle.However, disclose at present the diamond nano needle array in these work using main base It is easy to the characteristics of modifying in the excellent mechanical property of diamond and surface, diamond nano needle itself does not issue fluorescence, needs In its surface modification fluorescin as marking, not only operating process is cumbersome, to diamond nano wire surface bioprobe molecule The selectivity of modification and the sensitivity of detection can all produce serious influence.

Zero dimension diamond nano-particles and one-dimensional diamond nano structure are in drug delivery, bio-imaging and bio-sensing side Face shows more and more applications.The application of zero dimension diamond nano-particles is mainly using such as the special fluorescence radiation of NV colour center Characteristic, and the mechanical property that one-dimensional diamond vertical nanowires needle array structure mainly utilizes diamond excellent pierces through cell membrane and realizes Intracellular transmission and detection.Therefore, exploitation can have both the diamond of NV colour center and vertical arrangement nano needle arrays structure such as and receive Rice material studies the bio-sensing of cell interior, such as studies the variation tool of intracellular temperature, magnetic field and electro physiology property There are important scientific meaning and application value.Although there is trial to integrate such as NV colour center in one-dimensional diamond nano structure at present, But formed as NV colour center production rate it is low, depth distribution is dispersed very much, that is to say the colour center that can not form high quality.

Summary of the invention

It is an object of the invention to overcome the above-mentioned deficiency of the prior art, a kind of diamond nano needle construction and its system are provided Preparation Method and its application, can not integrate the colour center of diamond high quality to solve existing diamond nano needle, cause not have excellent The technical issues of different fluorescence radiation property and electron spin coherence.

In order to achieve the above-mentioned object of the invention, an aspect of of the present present invention provides a kind of diamond nano needle construction.The gold Hard rock nanometer needle construction includes that diamond body layer and several diamonds extended in the diamond body layer surface are received Rice needle, the adjacent diamond nano needle are spaced each other, and colour center structure is also distributed in diamond nano needle surface layer.

Another aspect of the present invention provides a kind of preparation method of diamond nano needle construction.The diamond nano The preparation method of needle construction includes the following steps:

Processing performed etching to diamond film layer, etching forms several diamond nano needles, the diamond nano needle that This interval；

In the diamond nano wire surface, successively one pure diamond layer of growth regulation, delta- doped layer and the second proof gold are rigid Rock layers；

Will growth have the delta- doped layer the diamond nano needle carry out electron beam irradiation processing after in protection It is made annealing treatment in property atmosphere.

Another aspect of the present invention provides the application method of above-mentioned diamond nano needle construction.Told diamond nano Needle construction is in fluorescence radiation probe, bio-sensing and the application into the device of Intracellular delivery substance.

Compared with prior art, above-mentioned diamond nano needle construction is by being distributed with colour center knot on diamond nano needle surface layer Structure, so that diamond nano needle construction of the present invention is assigned on the basis of with excellent mechanical property, also with excellent Fluorescence radiation property and electron spin coherence.Moreover, shallow-layer of the colour center structure distribution in diamond nano needle, to make It is uniform to obtain colour center structure distribution, and assigns diamond nano needle construction of the present invention excellent fluorescence and sensing capabilities.

Above-mentioned diamond nano needle construction preparation method by diamond nano needle surface layer successively grow diamond layer/ Delta- doped layer/diamond layer interlayer delta- doped diamond layer prepares shallow-layer colour center structure, achieves effective control The generation and distribution of colour center structure in Buddha's warrior attendant stone surface, to guarantee the intensity of colour center structure fluorescence radiation, stability and sensitive Degree.In this way, making the diamond nano needle construction of preparation that not only there is the mechanical property of diamond nano needle, but also have excellent Different fluorescence radiation property and electron spin coherence.In addition, each step of preparation method of the present invention can be controlled effectively, thus It ensure that the diamond nano needle construction performance of preparation is stablized, and high-efficient, it being capable of industrialized production.

Since colour center structure is also distributed in diamond nano needle surface layer in above-mentioned diamond nano needle construction, because This, can not only pierce through cell membrane for above-mentioned diamond nano needle construction and realize transmission and detection to intracellular matter, moreover it is possible to Enough realize has wider application in fields of biomedicine such as bio-sensing, bio-imagings, especially for detection nerve cell pair The reaction of environmental stimuli and the research of intracellular events provide a kind of effective means, promote diagnosis of nervous system diseases, treatment and The research and development of rehabilitation field.

Detailed description of the invention

Fig. 1 is the process flow diagram of diamond nano needle construction preparation method of the embodiment of the present invention；

Fig. 2 is the pure diamond successively grown in diamond nano needle construction preparation process in diamond nano wire surface Layer/delta- doped layer/pure diamond layer sandwich；

Fig. 3 is the enlarged drawing of part shown in A in Fig. 2；

Fig. 4 is diamond nano needle construction schematic diagram of the embodiment of the present invention.

Specific embodiment

In order to which technical problems, technical solutions and advantageous effects to be solved by the present invention are more clearly understood, below in conjunction with Embodiment and attached drawing, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used To explain the present invention, it is not intended to limit the present invention.

On the one hand, the embodiment of the invention provides a kind of diamond nano needle constructions with colour center structure.The Buddha's warrior attendant Stone nanometer needle construction is as shown in figure 4, it includes diamond body layer 1 and extends on 1 surface of diamond body layer Several diamond nano needles 2.

Wherein, diamond body layer 1 contained by above-mentioned diamond nano needle construction at least has the surface combined.One implements In example, the diamond body layer 1 is electron level pure diamond thin slice or preferred orientation polycrystalline diamond thick film.Select such Diamond body layer, can effectively ensure that such as etching form diamond nano needle 2, avoid using CVD single-crystal diamond face The complicated processes and very limited size (usually 3-5mm) such as cutting, the thinned, polishing of etching faced, meet etching shape At diamond nano needle 2 for intracellular matter transmit and detect needs, while obtain diamond nano needle 2 be monocrystalline Structure, inside existing for impurity and defect it is considerably less, do not influence colour center center contained by 2 surface layer of diamond nano needle fluorescence hair Light and spin coherence.

Diamond nano needle 2 contained by above-mentioned diamond nano needle construction is extended from diamond body layer surface, Particularly extend from 1 surface of diamond body layer and along the direction away from 1 surface of diamond body layer, in other words, The diamond nano needle 2 and the angled angle in 1 surface of diamond body layer, the angular range of the angle can be routine Range, such as 60 ° to 90 °, in embodiments of the present invention preferably 90 °.

In addition, above-mentioned diamond nano needle 2 is distributed on the surface of above-mentioned diamond body layer 1, in other words, Adjacent diamond nano needle 2 is to be spaced each other two-by-two, and such as in one embodiment, above-mentioned several diamond nano needle 2 is constituted Diamond nano needle array.In a particular embodiment, the density which is distributed in diamond body layer 1 is 10⁴-10⁹Needle/cm².By controlling the distribution density of diamond nano needle 2, it can control and improve above-mentioned diamond nano needle construction Fluorescence and sensing capabilities and efficiency, it is disposable to improve transmitting physical efficiency and a large amount of cells such as a large amount of cells of single treatment Implement the efficiency of monitoring.

In one embodiment, the diameter of above-mentioned diamond nano needle 2 is 100-2000nm, is highly 2-10 μm.Another In embodiment, the vertical wide ratio of the above-mentioned diamond nano needle 2 is 10-70.Wherein, the diameter of the diamond nano needle 2 refers to gold The diameter of 2 body trunk portion of hard rock nanoneedle.

On the basis of the various embodiments described above, colour center structure 3 is also distributed in the surface layer of diamond nano needle 2, namely It is that distribution has colour center structure 3 in the shallow-layer on 2 surface of diamond nano needle.In one embodiment, colour center structure 3 is received in diamond The density of rice 2 surface layer of needle distribution is 1-5000/needle, preferred 500-5000/needle.Wherein, when colour center structure 3 concentrates on gold When the needle point position of hard rock nanoneedle 2, a small amount of distribution can be.In another embodiment, colour center structure 3 is away from diamond nano needle The distance on 2 surfaces is less than or equal to 100nm.Wherein, the distance it should be understood that geometry midpoint to a face distance, specifically Refer to the colour center structure 3 arrive 2 surface of diamond nano needle distance.In a particular embodiment, the colour center structure 3 be N, The colour center structure that at least one of Si, P, B doping are formed, it is specific such as NV colour center structure.

In this way, diamond nano needle 2 contained by diamond nano needle construction is not only indulged with high in the various embodiments described above Wide ratio, impurity and defect are few, and purity is high and preferably mono-crystalline structures have excellent mechanical property；At the same time, in diamond The colour center structure 3 that 2 shallow-layer of nanoneedle is distributed uniformly, has excellent fluorescence radiation property and electron spin coherence.And And it being capable of a large amount of cells of single treatment, transmitting physical efficiency height and the implementation monitoring of a large amount of cells.Therefore, above-mentioned diamond nano needle Structure has the efficiency of excellent fluorescence and sensing capabilities and processing cell simultaneously on the basis of with excellent mechanical performance It is high.

On the other hand, the embodiment of the invention also provides a kind of preparation sides about diamond nano needle construction described above Method.Diamond nano needle construction preparation method process flow described above is as described in Figure 1, in conjunction with Buddha's warrior attendant as in Figure 2-4 Stone nanometer needle construction, preparation method include the following steps:

Step S01. etches diamond film layer to form diamond nano needle: performing etching processing to diamond film layer, carves Erosion forms several diamond nano needles 2；

Step S02. diamond nano wire surface grow delta- doped layer: 2 surface of diamond nano needle according to The first pure diamond of secondary growth layer 31, delta- doped layer 32 and the second pure diamond layer 33；

Step S03. carries out electron beam irradiation and annealing to delta- doped layer: having the delta- to adulterate growth Behind vacancy needed for the diamond nano needle progress electron beam irradiation processing generation of layer forms colour center in protective atmosphere It is made annealing treatment.

Specifically, in above-mentioned steps S01, the diamond film layer is to be used to etching to form diamond nano needle 2.Pass through Etching processing, part especially there is defect part to be etched removing, to be formed on the etched surface of the diamond film layer Above-mentioned several diamond nano needles 2, the remaining diamond film layer that is not etched constitute carry the diamond nano needle 2 as Fig. 2, diamond body layer 1 described in 4.It should make several diamond nano needles 2 to be formed to each other by etching processing Every, and the side of diamond nano needle 2 is perpendicular to diamond body layer surface.Etch the method for forming diamond nano needle 2 It can be conventional lithographic method.In conjunction with the embodiment of the present invention, in an embodiment, the lithographic method is using ECR assisted microwave synthesis etc. Ion etching or ICP etching apparatus carry out nanolithographic construction to diamond film layer surface, wherein etching gas can be but not Only hydrogen, argon gas, oxygen, CF₄、SF₆Etc. at least one, can also be other common etching gas.Reactive ion etching Process is the process of a physical etchings and chemical etching while effect, needs to reach one by the adjusting of process conditions and allocates Weighing apparatus, the diamond nano needle of the available higher vertical wide ratio of lower air pressure in the ecr plasma, when Ar gas addition and The enhancing of microwave power is so that side wall is more vertical.Nano diamond and defect at grain boundary can be etched away first, most The diamond nano needle 2 obtained eventually.

Such as in one embodiment, when forming above-mentioned diamond nano needle 2 using ECR assisted microwave synthesis plasma etching method, The condition of the ECR assisted microwave synthesis plasma etching are as follows:

Total gas couette: 10-50sccm, Ar gas 0-50%, H₂Gas 50-100%, air pressure: (5-8) × 10^-3MTorr, it is micro- Wave power: 700-1000W, chip bench add DC negative bias voltage -190~-230V, and etch period is 2-6 hours, the magnetic field in the area ECR Intensity is 875 Gausses；

In a particular embodiment, the condition of above-mentioned ECR assisted microwave synthesis plasma etching are as follows: etching gas is hydrogen/argon gas, And hydrogen/argon flow: 11sccm/9sccm, total gas couette: 20sccm；Air pressure: (5-8) × 10^-3MTorr, microwave power: 700-1000W, chip bench add DC negative bias voltage -190~-230V, and etch period is 2-6 hours, and the magnetic field strength in the area ECR is 875 Gausses.

In another embodiment, when forming above-mentioned diamond nano needle 2 using ICP etching method, the condition of ICP etching Are as follows:

Utilize hydrogen, argon gas, oxygen, helium, nitrogen, gaseous carbon source, CF₄、C₄F₈And SF₆One of or it is a variety of be anti- Gas is answered, the flow of reaction gas is 5~200sccm, and reaction pressure is 0.1~10Pa, and the power of plasma is 500 ~3000W, the radio-frequency power on chip bench are 50~300W, and etch period is 10~600min.

ECR assisted microwave synthesis plasma etching or each parameter of ICP etching are controlled by above-mentioned, so that etching was formed Diamond nano needle 2 has higher vertical wide ratio, such as the etching formation such as diamond described in diamond nano needle construction above Nanoneedle 2,2 side wall of diamond nano needle for forming etching is perpendicular to 1 surface of diamond body layer.In addition, In plasma etch process, the bombardment on the molybdenum substrate holder surface around diamond film layer sample being etched due to ion pair and Sputtering effect can spontaneously form the exposure mask of molybdenum and molybdenum carbide particles as etching in diamond film layer surface.According to grinding for early period Study carefully work to show since there are more sp for the boundary of diamond negative electron affinity (NEA) and column structure²The spy of phase and defect Property, launching electronics are stronger during grain boundary is in etching such as RIE, ECR, ICP, and the non-uniform electric of generation is led Cause diamond and the exposure mask that spontaneously forms at grain boundary all can preferentially be etched, by the reaction condition to etching process into Row optimization, obtains the diamond nano needle 2 of high quality single crystal structure, and guarantees the high vertical wide ratio of diamond nanoneedle 2, and side wall is vertical With it is smooth.

In step S01, the diamond film layer being etched can select conventional diamond film, the opposite embodiment of the present invention For, in an embodiment, select electron level pure diamond thin slice or preferred orientation polycrystalline diamond thick film as the gold of etching Hard rock film layer is thinned, the process that polishing etc. is complicated and non-to avoid the cutting that is faced using CVD single-crystal diamond, etching Normal limited size (usually 3-5mm) meets the needs that diamond nano needle 2 is transmitted and detected for intracellular matter, together When the diamond nano needle 2 that obtains be mono-crystalline structures, side wall is smooth, and impurity existing for inside and defect are considerably less, does not influence NV The fluorescence radiation and spin coherence at center.

In one embodiment, above-mentioned preferred orientation polycrystalline diamond thick film can be prepared by the following method:

It is prepared using microwave plasma CVD (MPCVD) or hot-wire chemical gas-phase deposition (HFCVD), film Growth carries out bias auxiliary forming core early period first.By taking HFCVD as an example, using double bias hot-wire chemical gas-phase depositions, nucleation process In heated filament upper gate apply positive bias, substrate apply back bias voltage；For microwave plasma CVD, substrate applies back bias voltage. Methane ratio is slightly higher in nucleation process, and nucleation process is completed about after half an hour, closes grid bias power supply, adjusts methane concentration and its Condition of its technological parameter to suitable preferred orientation diamond film growth.It is selective first for [001] orientation diamond film Growth, so that<001>orientation of the diamond seed vertical substrate with higher of growth, then adjusting technological parameter makes { 001 } face expands growth, may finally obtain (001) preferred orientation diamond thin.

In specific embodiment, above-mentioned preferred orientation polycrystalline diamond thick film preparation is referred to step in Examples below 1 It is prepared by the method for S11.

It is successively first pure when etching 2 surface of diamond nano needle of formation in above-mentioned steps S01 in above-mentioned steps S02 After diamond layer 31, delta- doped layer 32 and the second pure diamond layer 33, then pure hard rock is grown on 2 surface of diamond nano needle Layer/delta- doped layer/pure diamond layer sandwich, as shown in Figures 2 and 3.

Wherein, one pure diamond layer 31 of growth regulation, the second pure diamond layer 33, which can use, can grow pure diamond Method, the method for growing delta- doped layer 32 can also be using the method that can grow delta- doped layer.In an embodiment In, the first pure diamond layer 31, delta- doped layer 32 and the second pure diamond layer 33 are that CVD method deposits to be formed, and specifically may be used With but not only formed using MPCVD method.

In one embodiment, using MPCVD method in 2 surface growth regulation one of diamond nano needle Pure diamond layer 31 and/or condition in 32 surface growth regulation of delta- doped layer, two pure diamond layer 33 are as follows:

Base vacuum > 10^-6Pa, 600~900 DEG C of underlayer temperature, diamond carbon source gas/hydrogen gaseous mixture total flow: 200~2000sccm, the wherein percentage by volume 0.01~0.5% of diamond carbon source gas, hydrogen volume percentage 99.5~ 99.9%, air pressure: 20~40Torr, microwave power: 500~1200W, sedimentation time 2-20 hours.

In specific embodiment, using one pure diamond layer 31 of MPCVD method growth regulation and/or The condition of two pure diamond layer 33 of growth regulation are as follows:

Base vacuum > 10^-6Pa, 800 DEG C of underlayer temperature, diamond carbon source gas/hydrogen flowing quantity ratio: 0.1sccm/ 400sccm, total gas couette: 400sccm, air pressure: 30Torr, microwave power: 1200W, sedimentation time 10 hours.

Above-mentioned rigid using one pure diamond layer 31 of MPCVD method growth regulation and the second proof gold In the method for rock layers 33, an embodiment, the diamond carbon source gas is at least one of methane, acetylene, acetone, ethyl alcohol. Wherein, the methane is¹²CH₄Isotope gas.Using¹²CH₄Isotope gas can effectively reduce spin as 1/2¹³C, And¹²The spin of C is zero, therefore¹²C cannot be by detections such as nuclear magnetic resonance.For¹²The diamond of C isotope purifying, color Coherence time of the heart and to move back phase time very long.It is adopted in the application that some spin coherences using the center NV are sensed With¹²The diamond of C purifying, to improve diamond nano needle fluorescence intensity and detectivity in bio-sensing.

In another embodiment, raw on 31 surface of the first pure diamond layer using MPCVD method In the condition of delta- doped layer 32 are as follows:

Base vacuum > 10^-6Pa, 600~900 DEG C of underlayer temperature, diamond carbon source gas/hydrogen/doped chemical gas Mixed gas total flow: 200~2000sccm, the percentage by volume 0.01~0.5% of the diamond carbon source gas, the hydrogen Air volume percentage 80~99%, the doped chemical and carbon mass ratio are 1~20% (1000~10000ppm), gas Pressure: 20~40Torr, microwave power: 500~1200W, sedimentation time 5~20 minutes；

In specific embodiment, using the raw condition in delta- doped layer 32 of MPCVD method Are as follows:

800 DEG C of underlayer temperature, diamond carbon source gas/hydrogen/doped chemical gas mixed gas total flow flow: 0.1sccm/390sccm/10sccm, total gas couette: 400sccm, air pressure: 30Torr, microwave power: 1200W.

In the above-mentioned method using MPCVD method growth delta- doped layer 32, one implements Example, the diamond carbon source gas are at least one of methane, acetylene, acetone, ethyl alcohol.Wherein, the methane is¹²CH₄Together The plain gas in position.

Another embodiment, growing the doped chemical used in the method for delta- doped layer 32 is in N, Si, P, B It is at least one.In specific embodiment, N can be N₂, specially¹⁵N₂.Using¹⁵N₂It can be avoided in diamond nano needle 2 in itself The influence of existing nitrogen-vacancy defect.The gaseous compound that Si can be Si provides, such as silane (SiH₄), trimethyl silane (TMS), ethyl orthosilicate etc..The gaseous compound that P can be P provides, such as phosphine (PH₃), trimethyl phosphine (TMP), phosphoric acid Trimethyl etc..The gaseous compound that B can be B provides, such as diborane (B₂H₆), trimethyl borine (TMB), trimethylborate etc..

Above by the condition of one pure diamond layer 31 of growth regulation, delta- doped layer 32 and the second pure diamond layer 33, The growth rate for controlling the first pure diamond layer 31, delta- doped layer 32 and the second pure diamond layer 33 is preferably slowly grown Rate (growth rate about 10nm/h in such as above-mentioned specific embodiment), epitaxial quality and thickness and delta- doped layer 32 are mixed Miscellaneous degree.To guarantee after above-mentioned steps S03 processing, so that the colour center structure 3 generated is equal in 2 shallow-layer of diamond nano needle Even distribution.And can by control doping to colour center structure 3 distribution density and depth in 2 shallow-layer of diamond nano needle, tool Body is by the density of colour center structure 3 and the deep-controlled density in the colour center structure 3 as described in diamond nano needle construction above And depth.Furthermore it is possible to be calibrated using ion microprobe (SIMS) to each layer growth thickness, and delta- is adulterated The doping concentration of layer 32 measures.

In above-mentioned steps S03, there is the diamond nano needle 2 of delta- doped layer to carry out electricity surface growth in step S02 After beamlet radiation treatment and annealing, colour center structure 3 is formed in its shallow-layer in 2 surface layer of diamond nano needle.Its In, after being handled using electron beam irradiation, so that vacancy needed for generation forms colour center structure 3 in delta- doped layer.Annealing Processing in delta- doped layer so that generate colour center structure 3.

In one embodiment, there is the Buddha's warrior attendant of delta- doped layer in step S03 using electron beam irradiation processing surface growth When stone nanoneedle 2, the condition of electron beam irradiation processing are as follows: irradiation energy 2-4MeV, dosage are (1-9) × 10¹⁴cm^-2；Such as tool In body embodiment, the condition of electron beam irradiation processing are as follows: irradiation energy 2MeV, dosage 10¹⁴cm^-2.Pass through high-power electron beam Vacancy needed for irradiation generation forms colour center, to improve the production rate of colour center structure 3.

In another embodiment, the temperature of the annealing is 800 DEG C or more, and the time is 2-4 hours.Such as specific implementation In example, the temperature of the annealing is 850 DEG C, and the time is 2 hours.It is effectively ensured under this condition in diamond nano needle 2 Colour center structure 3 is generated in shallow-layer.

In addition, the protective atmosphere in annealing can be argon gas protective atmosphere or vacuum protection atmosphere, with Guarantee the generation of colour center structure 3 in annealing.

It in a further embodiment, further include using to annealed processing after the annealing in step S03 The diamond nano needle carries out the step of oxidation processes in acid solution.Since surface termination is to the characteristics of luminescence of colour center structure 3 Influence is very big, obtains the oxygen terminal of surface negative potential using the oxidation processes, it is ensured that the stability of photoluminescence of colour center structure 3.In addition, It can use the measurement of optical detection magnetic resonance spectrum and colour center structure 3 contained by diamond nano needle construction prepared as above-mentioned preparation method Coherence time and sensitivity to electric field.

In a particular embodiment, the oxidation processes after the annealing in step S03 are will to move back through described The diamond nano needle of fire processing, which is placed in mix acid liquor, be heated to 200 DEG C, kept for 30 minutes or more, wherein institute State mix acid liquor include volume ratio be 1:(1-3): the H of (1-3)₂SO₄、HNO₃And HClO₄Mixed acid.Using the mix acid liquor With oxidation processes are carried out under the temperature and time, effectively obtain the oxygen terminal of 2 surface negative potential of diamond nano needle, colour center be provided The stability of photoluminescence of structure 3.

Therefore, above-mentioned diamond nano needle construction preparation method is by successively growing Buddha's warrior attendant on 2 surface layer of diamond nano needle Rock layers/delta- doped layer/diamond layer interlayer delta- doped diamond layer prepares shallow-layer colour center structure 3, and realization has The generation and distribution of colour center structure 3 in effect control Buddha's warrior attendant stone surface, to guarantee the intensity of 3 fluorescence radiation of colour center structure, stabilization Property and sensitivity.So that the diamond nano needle construction of preparation not only has the mechanical property of diamond nano needle 2, also have excellent Different fluorescence radiation property and electron spin coherence.In addition, above-mentioned each step of preparation method can be controlled effectively, to protect The diamond nano needle construction performance for having demonstrate,proved preparation is stablized, and high-efficient, being capable of industrialized production.

Another aspect, on the basis of above-mentioned diamond nano needle construction and preparation method thereof, the embodiment of the present invention is also mentioned A kind of device to Intracellular delivery substance is supplied.The apparatus may include the routine to Intracellular delivery material device is necessary Component, such as diamond nano needle construction component.But the diamond nano needle construction component is described above as shown in Figure 4 Diamond nano of embodiment of the present invention needle construction or the gold of diamond nano needle construction preparation method preparation by mentioned earlier Hard rock nanometer needle construction.In this way, as described above, diamond nano contained by diamond nano needle construction described above Needle 2 has high vertical wide ratio, and impurity and defect are few, and further preferably mono-crystalline structures have excellent power so that its surface is smooth Learn performance；At the same time, the colour center structure 3 being distributed in 2 shallow-layer of diamond nano needle uniformly, has excellent luminescence Matter and electron spin coherence.Therefore, above-mentioned diamond nano needle construction on the basis of with excellent mechanical performance simultaneously With excellent fluorescence and sensing capabilities.It is above-mentioned as a result, to contain diamond of the embodiment of the present invention as shown in Figure 4 described above The device to Intracellular delivery substance of nanometer needle construction can not only pierce through cell membrane realize transmission to intracellular matter and Detection, additionally it is possible to which realizing has wider application in fields of biomedicine such as bio-sensing, bio-imagings, especially for detection mind A kind of effective means is provided to the reaction of environmental stimuli and the research of intracellular events through cell, the nervous system disease is promoted to examine Disconnected, treatment and rehabilitation field research and development.

Now in conjunction with specific example, diamond nano needle construction of the embodiment of the present invention and preparation method thereof is carried out further detailed It describes in detail bright.

Embodiment 1

The present embodiment provides a kind of diamond nano needle constructions and preparation method thereof.The knot of the diamond nano needle construction Structure is as shown in Figure 4 comprising diamond body layer 1 and several diamonds extended on 1 surface of diamond body layer 2 array of nanoneedle, adjacent diamond nanoneedle 2 are spaced each other, and the side of diamond nano needle 2 is perpendicular to diamond body layer Colour center structure 3 is also distributed in 1 surface layer of diamond nano needle in 1 surface.

The present embodiment diamond nano needle construction the preparation method is as follows:

S11. the deposition preferred orientation diamond film layer on silicon substrate surface is prepared:

Microwave plasma CVD technique is selected to prepare 5-10 microns of thick diamonds on 1-5cm × 1-5cm, (001) silicon wafer Film layer.Silicon wafer is placed in hydrofluoric acid solution before growth and is impregnated 2 minutes, the oxide layer on surface is removed, is then put into silicon wafer It is cleaned by ultrasonic 10 minutes in acetone soln, is cleaned by ultrasonic 10 minutes in deionized water, is cleaned by ultrasonic 10 minutes in alcoholic solution；It will Silicon wafer matrix after cleaning is placed on molybdenum chip bench, and is put in CVD equipment, is evacuated to 10^-5Pa or less；Before film growth The residual oxidization layer of silicon chip surface and other impurity are cleaned again with hydrogen plasma: air pressure: 30Torr, microwave power: 1200W, silicon substrate temperature: 800 DEG C, the time 30 minutes.Then begin to diamond thin forming core stage, microwave plasma CVD Design parameter it is as follows: methane/hydrogen flowing quantity: 10sccm/190sccm, total gas couette: 200sccm, air pressure: 16Torr, it is micro- Wave power: 800W, silicon substrate temperature: 800 DEG C, Substrate negative bias voltage: -150V, nucleated time: 12 minutes.Microwave plasma CVD In (001) preferred orientation diamond film growth design parameter are as follows: methane/hydrogen flowing quantity: 1.5sccm/298sccm, total gas Body flow: 300sccm, air pressure: 30Torr, microwave power: 1200W, silicon substrate temperature: 850 DEG C, sedimentation time: 10 hours；

S12. diamond film layer is etched to form diamond nano needle array 2:

Diamond thick-film closes microwave power supply and gas source after growing, and is down to room temperature to underlayer temperature, is evacuated to 10^- ⁵Then Pa is flushed with hydrogen gas to 7 millitorrs again, opens ECR microwave plasma bulk-mode, the magnetic field that additional electromagnetic coil provides is in ECR The intensity in area is 875 Gausses, and the design parameter that reactive ion etching is carried out in ECR assisted microwave synthesis plasma is as follows: hydrogen/argon Throughput: 11sccm/9sccm, total gas couette: 20sccm, air pressure: 7 × 10^-3MTorr, microwave power: 800W, chip bench add DC negative bias voltage -200V, etch period are 2 hours；Turn off bias, microwave power supply, electromagnetic coil power supply after etching, closes Gas obtains single-crystal diamond nano needle arrays 2；

S13. delta doped diamond layer is grown on 2 surface of diamond nano needle array:

Directly in microwave plasma CVD Working mould after the completion of reactive ion etching prepares diamond nano needle array 2 Continued growth delta- doped diamond layer under formula；It is grown outside one layer of high-purity on the surface of diamond nano needle array 2 first Prolong diamond layer 31, is used in growth course¹²CH₄Isotope gas (purity 99.999%), in order to obtain higher extension matter Amount, using slowly growth conditions, growth rate about 10nm/h, concrete technology condition is as follows: base vacuum > 10^-6Pa, 800 DEG C of underlayer temperature, methane/hydrogen gas flow-rate ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, sedimentation time 5 hours；Then nitrogen doped layer is grown on 31 surface of high-purity epitaxial diamond layer 32, it uses¹⁵N₂The process conditions of isotope gas (purity > 98%) doped growing are as follows: 800 DEG C of underlayer temperature, methane/hydrogen/ Nitrogen flow: 0.1sccm/390sccm/10sccm, total gas couette: 400sccm, air pressure: 30Torr, microwave power: 1200W, sedimentation time 0.5 hour；A high-purity epitaxial diamond layer 33, the condition of growth are as follows: substrate temperature are finally carried out again 800 DEG C of degree, methane/hydrogen gas flow-rate ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave Power 1200W, sedimentation time 5 hours；Structure such as Fig. 2 of final growth 31/ nitrogen doped layer of diamond layer, 32/ diamond layer 33 and Shown in Fig. 3；

S14. post-processing obtains the diamond nano needle at the center shallow-layer NV 3:

There is the diamond nano needle array 2 of delta doped diamond layer to pass through high-energy electron beam irradiation step S14 growth Vacancy needed for generation forms NV colour center 3, irradiation energy 2MeV, dosage 10¹⁴cm^-2；It is then annealed and is produced by high-temperature vacuum Raw NV colour center, vacuum annealing furnace temperature are maintained at 850 DEG C two hours, are 1:1:1 by diamond nano needle array merging volume ratio H₂SO₄:HNO₃:HClO₄Middle heating is boiled to 200 DEG C, kept for 30 minutes or more, it obtains the diamond that surface is oxygen terminal and receives Rice needle, it is ensured that the stability of NV colour center negative potential.

Embodiment 2

Microwave plasma CVD technique is selected to prepare 5-10 microns of thick diamonds on 1-5cm × 1-5cm, (001) silicon wafer Film layer.Silicon wafer is placed in hydrofluoric acid solution before growth and is impregnated 2 minutes, the oxide layer on surface is removed, is then put into silicon wafer It is cleaned by ultrasonic 10 minutes in acetone soln, is cleaned by ultrasonic 10 minutes in deionized water, is cleaned by ultrasonic 10 minutes in alcoholic solution；It will Silicon wafer matrix after cleaning is placed on molybdenum chip bench, and is put in CVD equipment, is evacuated to 10^-5Pa or less；Before film growth The residual oxidization layer of silicon chip surface and other impurity are cleaned again with hydrogen plasma: air pressure: 30Torr, microwave power: 1200W, silicon substrate temperature: 800 DEG C, the time 30 minutes.Then begin to diamond thin forming core stage, microwave plasma CVD Design parameter it is as follows: methane/hydrogen flowing quantity: 10sccm/190sccm, total gas couette: 200sccm, air pressure: 16Torr, it is micro- Wave power: 800W, silicon substrate temperature: 800 DEG C, Substrate negative bias voltage: -150V, nucleated time: 12 minutes.Microwave plasma CVD In (001) preferred orientation diamond film growth design parameter are as follows: methane/hydrogen flowing quantity: 1.5sccm/298sccm, total gas Body flow: 300sccm, air pressure: 30Torr, microwave power: 1200W, silicon substrate temperature: 850 DEG C, sedimentation time: 20 hours；

S12. diamond film layer is etched to form diamond nano needle array 2:

Diamond thick-film closes microwave power supply and gas source after growing, and is down to room temperature to underlayer temperature, is evacuated to 10^- ⁵Then Pa is flushed with hydrogen gas to 7 millitorrs again, opens ECR microwave plasma bulk-mode, the magnetic field that additional electromagnetic coil provides is in ECR The intensity in area is 875 Gausses, and the design parameter that reactive ion etching is carried out in ECR assisted microwave synthesis plasma is as follows: hydrogen/argon Throughput: 11sccm/9sccm, total gas couette: 20sccm, air pressure: 7 × 10^-3MTorr, microwave power: 800W, chip bench add DC negative bias voltage -230V, etch period are 4 hours；Turn off bias, microwave power supply, electromagnetic coil power supply after etching, closes Gas obtains single-crystal diamond nano needle arrays 2；

Directly in microwave plasma CVD Working mould after the completion of reactive ion etching prepares diamond nano needle array 2 Continued growth delta- doped diamond layer under formula；It is grown outside one layer of high-purity on the surface of diamond nano needle array 2 first Prolong diamond layer 31, is used in growth course¹²CH₄Isotope gas (purity 99.999%), in order to obtain higher extension matter Amount, using slowly growth conditions, growth rate about 10nm/h, concrete technology condition is as follows: base vacuum > 10^-6Pa, 800 DEG C of underlayer temperature, methane/hydrogen gas flow-rate ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, sedimentation time 10 hours；Then N doping is grown on 31 surface of high-purity epitaxial diamond layer Layer 32 uses¹⁵N₂The process conditions of isotope gas (purity > 98%) doped growing are as follows: 800 DEG C of underlayer temperature, methane/hydrogen Gas/nitrogen flow: 0.1sccm/390sccm/10sccm, total gas couette: 400sccm, air pressure: 30Torr, microwave power: 1200W, sedimentation time 0.5 hour；A high-purity epitaxial diamond layer 33, the condition of growth are as follows: substrate temperature are finally carried out again 800 DEG C of degree, methane/hydrogen gas flow-rate ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave Power 1200W, sedimentation time 10 hours；Structure such as Fig. 2 of final growth 31/ nitrogen doped layer of diamond layer, 32/ diamond layer 33 With shown in Fig. 3；

Embodiment 3

S12. diamond film layer is etched to form diamond nano needle array 2:

Directly in microwave plasma CVD Working mould after the completion of reactive ion etching prepares diamond nano needle array 2 Continued growth delta- doped diamond layer under formula；It is grown outside one layer of high-purity on the surface of diamond nano needle array 2 first Prolong diamond layer 31, is used in growth course¹²CH₄Isotope gas (purity 99.999%), in order to obtain higher extension matter Amount, using slowly growth conditions, growth rate about 10nm/h, concrete technology condition is as follows: base vacuum > 10^-6Pa, 800 DEG C of underlayer temperature, methane/hydrogen gas flow-rate ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, sedimentation time 5 hours；Then nitrogen doped layer is grown on 31 surface of high-purity epitaxial diamond layer 32, it uses¹⁵N₂The process conditions of isotope gas (purity > 98%) doped growing are as follows: 800 DEG C of underlayer temperature, methane/hydrogen/ Nitrogen flow: 0.1sccm/300sccm/100sccm, total gas couette: 400sccm, air pressure: 30Torr, microwave power: 1200W, sedimentation time 1 hour；A high-purity epitaxial diamond layer 33, the condition of growth are as follows: underlayer temperature are finally carried out again 800 DEG C, methane/hydrogen gas flow-rate ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave function Rate 1200W, sedimentation time 20 hours；Structure such as Fig. 2 of final growth 31/ nitrogen doped layer of diamond layer, 32/ diamond layer 33 and Shown in Fig. 3；

Embodiment 4

S12. diamond film layer is etched to form diamond nano needle array 2:

Directly in microwave plasma CVD Working mould after the completion of reactive ion etching prepares diamond nano needle array 2 Continued growth delta- doped diamond layer under formula；It is grown outside one layer of high-purity on the surface of diamond nano needle array 2 first Prolong diamond layer 31, is used in growth course¹²CH₄Isotope gas (purity 99.999%), in order to obtain higher extension matter Amount, using slowly growth conditions, growth rate about 10nm/h, concrete technology condition is as follows: base vacuum > 10^-6Pa, 800 DEG C of underlayer temperature, methane/hydrogen gas flow-rate ratio: 1.5sccm/298sccm, total gas couette 300sccm, air pressure 30Torr, microwave power 1200W, sedimentation time 10 minutes；Then N doping is grown on 31 surface of high-purity epitaxial diamond layer Layer 32 uses¹⁵N₂The process conditions of isotope gas (purity > 98%) doped growing are as follows: 800 DEG C of underlayer temperature, methane/hydrogen Gas/nitrogen flow: 1.5sccm/258sccm/40sccm, total gas couette: 300sccm, air pressure: 30Torr, microwave power: 1200W, sedimentation time 2 minutes；A high-purity epitaxial diamond layer 33, the condition of growth are as follows: underlayer temperature are finally carried out again 800 DEG C, methane/hydrogen gas flow-rate ratio: 1.5sccm/298sccm, total gas couette 300sccm, air pressure 30Torr, microwave function Rate 1200W, sedimentation time 10 minutes；Structure such as Fig. 2 of final growth 31/ nitrogen doped layer of diamond layer, 32/ diamond layer 33 and Shown in Fig. 3；

Embodiment 5

S12. diamond film layer is etched to form diamond nano needle array 2:

Directly in microwave plasma CVD Working mould after the completion of reactive ion etching prepares diamond nano needle array 2 Continued growth delta- doped diamond layer under formula；It is grown outside one layer of high-purity on the surface of diamond nano needle array 2 first Prolong diamond layer 31, is used in growth course¹²CH₄Isotope gas (purity 99.999%), in order to obtain higher extension matter Amount, using slowly growth conditions, growth rate about 10nm/h, concrete technology condition is as follows: base vacuum > 10^-6Pa, 800 DEG C of underlayer temperature, methane/hydrogen gas flow-rate ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, sedimentation time 5 hours；Then silicon doped layer is grown on 31 surface of high-purity epitaxial diamond layer 32, it uses²⁹SiH₄Isotope gas (purity > 98%), silane gas used herein are silane/hydrogen mixing carrier gas Body, wherein the concentration of silane is 1%.The process conditions of doped growing are as follows: 800 DEG C of underlayer temperature, methane/hydrogen/silane flow rate: 0.1sccm/390sccm/10sccm, total gas couette: 400sccm, air pressure: 30Torr, microwave power: 1200W, sedimentation time 1 hour；A high-purity epitaxial diamond layer 33, the condition of growth are finally carried out again are as follows: 800 DEG C of underlayer temperature, methane/hydrogen Gas flow ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, when deposition Between 10 hours；The structure of final growth 31/ silicon doped layer of diamond layer, 32/ diamond layer 33 is as shown in Figures 2 and 3；

There is the diamond nano needle array 2 of delta doped diamond layer to pass through high-energy electron beam irradiation step S14 growth Vacancy needed for generation forms SiV colour center 3, irradiation energy 2MeV, dosage 10¹⁴cm^-2；Then annealed by high-temperature vacuum SiV colour center is generated, it is 1 by diamond nano needle array merging volume ratio that vacuum annealing furnace temperature, which is maintained at 850 DEG C two hours: The H of 1:1₂SO₄:HNO₃:HClO₄Middle heating is boiled to 200 DEG C, kept for 30 minutes or more, obtain the diamond that surface is oxygen terminal Nanoneedle, it is ensured that the stability of SiV colour center negative potential.

Embodiment 6

S12. diamond film layer is etched to form diamond nano needle array 2:

Directly in microwave plasma CVD Working mould after the completion of reactive ion etching prepares diamond nano needle array 2 Continued growth delta- doped diamond layer under formula；It is grown outside one layer of high-purity on the surface of diamond nano needle array 2 first Prolong diamond layer 31, is used in growth course¹²CH₄Isotope gas (purity 99.999%), in order to obtain higher extension matter Amount, using slowly growth conditions, growth rate about 10nm/h, concrete technology condition is as follows: base vacuum > 10^-6Pa, 800 DEG C of underlayer temperature, methane/hydrogen gas flow-rate ratio: 0.2sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, sedimentation time 5 hours；Then nitrogen doped layer is grown on 31 surface of high-purity epitaxial diamond layer 32, it uses¹¹B isotope trimethyl borane gases (purity > 98%), trimethyl borane gases used herein are trimethyl borine Alkane/hydrogen mixing diluent gas, wherein the concentration of trimethyl borine is 0.1%.The process conditions of doped growing are as follows: substrate temperature 800 DEG C of degree, methane/hydrogen/trimethyl borine flow: 0.1sccm/390sccm/10sccm, total gas couette: 400sccm, gas Pressure: 30Torr, microwave power: 1200W, sedimentation time 1 hour；Finally a high-purity epitaxial diamond layer 33 is carried out again, it is raw Long condition are as follows: 800 DEG C of underlayer temperature, methane/hydrogen gas flow-rate ratio: 0.2sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, sedimentation time 10 hours；Final growth 31/ boron-dopped layer of diamond layer The structure of 32/ diamond layer 33 is as shown in Figures 2 and 3；

There is the diamond nano needle array 2 of delta doped diamond layer to pass through high-energy electron beam irradiation step S14 growth Vacancy needed for generation forms BV colour center 3, irradiation energy 2MeV, dosage 10¹⁴cm^-2；It is then annealed and is produced by high-temperature vacuum Raw BV colour center, vacuum annealing furnace temperature are maintained at 850 DEG C two hours, are 1:1:1 by diamond nano needle array merging volume ratio H₂SO₄:HNO₃:HClO₄Middle heating is boiled to 200 DEG C, kept for 30 minutes or more, it obtains the diamond that surface is oxygen terminal and receives Rice needle, it is ensured that the stability of BV colour center negative potential.

Embodiment 7

S12. diamond film layer is etched to form diamond nano needle array 2:

Directly in microwave plasma CVD Working mould after the completion of reactive ion etching prepares diamond nano needle array 2 Continued growth delta- doped diamond layer under formula；It is grown outside one layer of high-purity on the surface of diamond nano needle array 2 first Prolong diamond layer 31, is used in growth course¹²CH₄Isotope gas (purity 99.999%), in order to obtain higher extension matter Amount, using slowly growth conditions, growth rate about 10nm/h, concrete technology condition is as follows: base vacuum > 10^-6Pa, 800 DEG C of underlayer temperature, methane/hydrogen gas flow-rate ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, sedimentation time 10 hours；Then phosphorus doping is grown on 31 surface of high-purity epitaxial diamond layer Layer 32, using PH₄Isotope gas (purity > 98%), silane gas used herein are phosphine/hydrogen mixing carrier gas Body, wherein the concentration of phosphine is 1%.The process conditions of doped growing are as follows: 800 DEG C of underlayer temperature, methane/hydrogen/phosphine flow: 0.1sccm/390sccm/10sccm, total gas couette: 400sccm, air pressure: 30Torr, microwave power: 1200W, sedimentation time 1 hour；A high-purity epitaxial diamond layer 33, the condition of growth are finally carried out again are as follows: 800 DEG C of underlayer temperature, methane/hydrogen Gas flow ratio: 0.1sccm/400sccm, total gas couette 400sccm, air pressure 30Torr, microwave power 1200W, when deposition Between 10 hours；The structure of final growth 31/ phosphorus doping layer of diamond layer, 32/ diamond layer 33 is as shown in Figures 2 and 3；

S14. post-processing obtains the diamond nano needle at the center shallow-layer PV 3:

There is the diamond nano needle array 2 of delta doped diamond layer to pass through high-energy electron beam irradiation step S14 growth Vacancy needed for generation forms PV colour center 3, irradiation energy 2MeV, dosage 10¹⁴cm^-2；It is then annealed and is produced by high-temperature vacuum Raw PV colour center, vacuum annealing furnace temperature are maintained at 850 DEG C two hours, are 1:1:1 by diamond nano needle array merging volume ratio H₂SO₄:HNO₃:HClO₄Middle heating is boiled to 200 DEG C, kept for 30 minutes or more, it obtains the diamond that surface is oxygen terminal and receives Rice needle, it is ensured that the stability of PV colour center negative potential.

Correlated performance test:

The diamond nano needle construction that above-described embodiment 1-7 is provided carries out the survey such as correlated performance in following table 1 respectively Examination:

Table 1

It is excellent by above-mentioned table 1 it is found that diamond nano needle construction provided in an embodiment of the present invention has high vertical wide ratio Fluorescence radiation performance and electron spin coherence can pierce through for the embodiment of the present invention to the device of Intracellular delivery substance Cell membrane realizes transmission and detection to intracellular matter, additionally it is possible to realize in the biomedical neck such as bio-sensing, bio-imaging Domain, which is widely applied, provides guarantee.

The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims

1. a kind of diamond nano needle construction extends including diamond body layer and in the diamond body layer surface Several diamond nano needles, it is characterised in that: the adjacent diamond nano needle is spaced each other, and the diamond nano needle hangs down Directly in the diamond body layer surface, colour center structure is also distributed in diamond nano needle surface layer.

2. diamond nano needle construction according to claim 1, it is characterised in that: the colour center structure is in the diamond The density of nanoneedle surface layer distribution is 1-5000/needle；And/or

Distance of the colour center structure away from the diamond nano wire surface is less than or equal to 100nm；And/or

The colour center structure is the colour center structure that at least one of N, Si, P, B doping are formed.

3. diamond nano needle construction according to claim 1 or 2, it is characterised in that: the diamond nano needle it is straight Diameter is 100-2000nm, is highly 2-10 μm；Or it is vertical wide than being 10-70.

4. a kind of preparation method of diamond nano needle construction, includes the following steps:

Processing is performed etching to diamond film layer, etching forms several diamond nano needles, and the diamond nano needle is to each other Every；

In the diamond nano wire surface successively one pure diamond layer of growth regulation, delta- doped layer and the second pure diamond Layer；

Will growth have the delta- doped layer the diamond nano needle carry out electron beam irradiation processing after in protectiveness gas It is made annealing treatment in atmosphere.

5. the preparation method according to claim 4, it is characterised in that: growth the first pure diamond layer, described second Pure diamond layer, the delta- doped layer deposit to be formed using CVD method, wherein grow the condition of the delta- doped layer Are as follows:

Base vacuum > 10^-6Pa, 600~900 DEG C of underlayer temperature, diamond carbon source gas/hydrogen/doped chemical gas mixing Total gas flow rate: 200~2000sccm, the percentage by volume 0.01~0.5% of the diamond carbon source gas, the hydrogen Product percentage 80~99%, the doped chemical and carbon mass ratio are 1%~20%, air pressure: 20~40Torr, microwave Power: 500~1200W, sedimentation time 5~30 minutes；

Grow the condition of the first pure diamond layer and/or the second pure diamond layer are as follows:

Base vacuum > 10^-6Pa, 600~900 DEG C of underlayer temperature, diamond carbon source gas/hydrogen gaseous mixture total flow: 200~ 2000sccm, the wherein percentage by volume 0.01~0.5% of diamond carbon source gas, hydrogen volume percentage 99.5~ 99.9%, air pressure: 20~40Torr, microwave power: 500~1200W, sedimentation time 2-20 hours.

6. preparation method according to claim 5, it is characterised in that: the doped chemical is at least one in N, Si, P, B Kind.

7. preparation method according to claim 6, it is characterised in that: the N doped chemical is¹⁵N；

The source Si of the Si doped chemical is at least one of silane, trimethyl silane, ethyl orthosilicate；

The source P of the P doped chemical is at least one of phosphine, trimethyl silicane phosphine, trimethyl phosphate；

The source B of the B doped chemical is at least one of diborane, trimethyl borine, trimethylborate.

8. preparation method according to claim 5, it is characterised in that: the diamond carbon source gas is methane, acetylene, third At least one of ketone, ethyl alcohol.

9. according to any preparation method of claim 5-8, it is characterised in that: the irradiation energy of the electron beam irradiation processing Amount is 2~4MeV, and dosage is (1~9) × 10¹⁴cm^-2；And/or

The temperature of the annealing is 800~1000 DEG C, and the time is 2~4 hours.

10. according to any preparation method of claim 5-8, it is characterised in that: carried out to the diamond nano needle After annealing, further include the steps that carrying out oxidation processes in acid solution to the diamond nano needle.

11. preparation method according to claim 10, it is characterised in that: the oxidation processes are will be through the annealing The diamond nano needle be placed in mix acid liquor and carry out heating and boil to 200~350 DEG C, kept for 30 minutes or more, wherein The mix acid liquor includes that volume ratio is 1:(1-3): the H of (1-3)₂SO₄、HNO₃And HClO₄Mixed acid.

12. according to claim 5-8,11 any preparation methods, it is characterised in that: carved to the diamond film layer The method for losing processing is as follows:

Diamond film layer is etched using ECR assisted microwave synthesis plasma etching or ICP；Wherein,

The condition of the ECR assisted microwave synthesis plasma etching are as follows:

Total gas couette: 20sccm, etching gas H₂Volume fraction 50~100%, Ar volume fraction 0~50%, air pressure: (5-8) ×10^-3MTorr, microwave power: 700-1000W, chip bench add DC negative bias voltage -190~-230V, and etch period is that 2-8 is small When, the magnetic field strength in the area ECR is 875 Gausses；

The condition of the ICP etching are as follows:

Utilize hydrogen, argon gas, oxygen, helium, nitrogen, gaseous carbon source, CF₄、C₄F₈And SF₆One of or it is a variety of be reaction gas Body, the flow of reaction gas are 5~200sccm, and reaction pressure is 0.1~10Pa, the power of plasma is 500~ 3000W, the radio-frequency power on chip bench are 50~300W, and etch period is 10~600min.

13. preparation method according to claim 12, it is characterised in that: the etching gas hydrogen, argon gas, oxygen, CF₄、 SF₆One or more of mixed gas.

14. preparation method according to claim 12, it is characterised in that: the diamond film layer is electron level purity Buddha's warrior attendant Stone thin slice or preferred orientation polycrystalline diamond thick film.

15. diamond nano needle construction according to claim 1 to 4 is in fluorescence radiation probe, bio-sensing and to thin Application in the device of delivered substance intracellular.