CN112744791B - Metal oxide nanoparticles, method for producing same and use thereof - Google Patents
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Abstract
The invention provides a preparation method of metal oxide nanoparticles, which comprises the following steps: providing a compound of formula X-C 6 H 4 ‑N‑N‑C 6 H 3 An organic reagent of OH-Y and a metal oxide nanoparticle sample to be treated; X-C 6 H 4 ‑N‑N‑C 6 H 3 In OH-Y, X is alkane, and Y is selected from hydrocarbon group containing at least one sulfhydryl group; and mixing the organic reagent and the metal oxide nanoparticle sample in a liquid phase medium, and adding an inorganic salt reducing agent to prepare the metal oxide nanoparticles.
Description
Technical Field
The invention belongs to the field of metal oxide nanoparticles, and particularly relates to a metal oxide nanoparticle and a preparation method and application thereof.
Background
Metal oxide nanoparticles (quatum dots) are semiconductor nanostructures that confine excitons in three spatial directions. With the development of metal oxide nanoparticle technology, the application of metal oxide nanoparticles has penetrated into many fields, especially in the fields of quantum dot light-emitting diodes, solar cells, biomarkers, and the like.
The quantum dot light-emitting diode has the characteristics of high color purity, adjustable light-emitting wavelength, high driving efficiency and the like, and is an important development technology of the future display industry. As the technology advances, the commercialization level of the quantum dot light emitting diode gradually increases, but there still exist many problems such as unstable device efficiency, poor lifetime, etc., and the main factor affecting the above-mentioned performance of the quantum dot light emitting diode device is the imbalance of charge injection of the device.
Disclosure of Invention
The invention aims to provide a metal oxide nanoparticle, a preparation method and application thereof, and aims to solve the problem of unbalanced charge injection of the conventional quantum dot light-emitting diode.
In order to achieve the purpose, the invention adopts the following technical scheme:
the first aspect of the present invention provides a method for preparing metal oxide nanoparticles, comprising the steps of:
providing a compound of formula X-C 6 H 4 -N-N-C 6 H 3 An organic reagent of OH-Y and a metal oxide nanoparticle sample to be treated; X-C 6 H 4 -N-N-C 6 H 3 In OH-Y, X is alkane, and Y is selected from hydrocarbon group containing at least one sulfhydryl group;
and mixing the organic reagent and the metal oxide nanoparticle sample in a liquid phase medium, and adding an inorganic salt reducing agent to prepare the metal oxide nanoparticles.
In a second aspect, the present invention provides a metal oxide nanoparticle, which is the metal oxide nanoparticle prepared by the above method.
The invention provides a quantum dot light-emitting diode, which comprises a cathode and an anode which are oppositely arranged, a quantum dot light-emitting layer arranged on the cathode and the anode, and an electron transmission layer arranged between the cathode and the quantum dot light-emitting layer, wherein part or all of the material of the electron transmission layer is the metal oxide nanoparticles prepared by the method or the metal oxide nanoparticles.
The preparation method of the metal oxide nano-particles provided by the invention comprises the steps of firstly, obtaining a molecular formula of X-C 6 H 4 -N-N-C 6 H 3 Mixing OH-Y organic reagent with metal oxide nanoparticle sample to be treated, adding inorganic salt reducing agent containing-C 6 H 4 -N-N-C 6 H 3 Said X-C of OH- 6 H 4 -N-N-C 6 H 3 OH-Y is decomposed into two organic molecules X-C under the action of inorganic salt reducing agent 6 H 4 -NH 2 And H 2 N-C 6 H 3 OH-Y. Disassembled H 2 N-C 6 H 3 The mercapto functional group in OH-Y combines with the metal element on the surface of the metal oxide nanoparticle sample, thereby combining H 2 N-C 6 H 3 OH-Y is connected on the surface of the metal oxide nano-particles. The obtained water-phase metal oxide nanoparticles with the surfaces containing benzene rings and hydroxyl groups have a strong electron-withdrawing function, so that the electron transfer efficiency of the metal oxide nanoparticles can be improved.
The metal oxide nano-particles provided by the invention have excellent electron transmission efficiency because the surfaces of the particles contain electron-withdrawing benzene rings and hydroxyl groups.
According to the quantum dot light-emitting diode provided by the invention, as the electron transport layer material contains or is completely provided with the metal oxide nanoparticles, the charge injection balance can be obviously improved, and the luminous efficiency and the service life of the quantum dot light-emitting diode are improved.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required to be used in the embodiments or the prior art description will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings may be obtained according to these drawings without inventive labor.
Fig. 1 is a schematic flow chart of a method for preparing metal oxide nanoparticles according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
With reference to fig. 1, a first aspect of the embodiments of the present invention provides a method for preparing metal oxide nanoparticles, including the following steps:
S01. providing a compound of formula X-C 6 H 4 -N-N-C 6 H 3 An organic reagent of OH-Y and a metal oxide nanoparticle sample to be treated; X-C 6 H 4 -N-N-C 6 H 3 In OH-Y, X is alkane, and Y is selected from hydrocarbon group containing at least one sulfhydryl group;
s02, mixing the organic reagent and the metal oxide nano-particle sample in a liquid phase medium, and adding an inorganic salt reducing agent to prepare the metal oxide nano-particle.
The preparation method of the metal oxide nano-particles provided by the embodiment of the invention firstly adopts the molecular formula of X-C 6 H 4 -N-N-C 6 H 3 Mixing OH-Y organic reagent with metal oxide nanoparticle sample to be treated, adding inorganic salt reducing agent containing-C 6 H 4 -N-N-C 6 H 3 Said X-C of OH- 6 H 4 -N-N-C 6 H 3 OH-Y is decomposed into two organic molecules X-C under the action of inorganic salt reducing agent 6 H 4 -NH 2 And H 2 N-C 6 H 3 OH-Y. Disassembled H 2 N-C 6 H 3 The mercapto functional group in OH-Y combines with the metal element on the surface of the metal oxide nanoparticle sample, thereby combining H 2 N-C 6 H 3 OH-Y is connected on the surface of the metal oxide nano-particles. The obtained water-phase metal oxide nanoparticles with the surfaces containing benzene rings and hydroxyl groups have a strong electron-withdrawing function, so that the electron transfer efficiency of the metal oxide nanoparticles can be improved.
Specifically, in step S01, the metal oxide nanoparticle sample is aqueous phase metal oxide nanoparticles selected from ZnO, niO, and W 2 O 3 、Mo 2 O 3 、TiO 2 、SnO、ZrO 2 、Ta 2 O 3 But is not limited thereto. Further, the surface of the water phase metal nano-particle contains a ligand, and the ligand is selected from- (CH) 2 ) p -OH、-(CH 2 ) p -COOH、-(CH 2 ) p -NH 2 One ofWherein the value of p is an integer of 0 to 18.
The molecular formula is X-C 6 H 4 -N-N-C 6 H 3 Organic reagent of OH-Y containing-C 6 H 4 -N-N-C 6 H 3 OH-structure which can be dissociated into-C by the action of an inorganic reducing agent 6 H 4 -NH 2 And H 2 N-C 6 H 3 OH-, in which H 2 N-C 6 H 3 OH < - > is connected with Y containing sulfydryl and can be combined with a metal oxide nanoparticle sample, so that hydroxyl and phenyl on the surface of the metal oxide nanoparticle sample are endowed, and the electron transport performance of the metal oxide nanoparticles is improved.
The molecular formula is X-C 6 H 4 -N-N-C 6 H 3 OH-Y, wherein Y is selected from hydrocarbon groups having at least one thiol group for binding the metal of the metal oxide nanoparticle sample, preferably an alkane group having a thiol group. Preferably, Y is an alkane structure of a hydrocarbon backbone, which is free of functional groups other than SH, thereby avoiding the introduction of other functional groups or complex structures that affect the formula X-C 6 H 4 -N-N-C 6 H 3 Organic reagent of OH-Y and metal oxide nanoparticle sample with molecular formula of X-C 6 H 4 -N-N-C 6 H 3 The reaction of organic reagent of OH-Y and inorganic salt reducing agent hinders the introduction of electron-withdrawing functional group on the surface of metal oxide nano-particle. Further preferably, Y is selected from- (CH) 2 ) m The value of m is selected from an integer of 1-18, and the organic reagent with m in the range has proper viscosity, so that the subsequent reaction can be smoothly carried out in a liquid phase state.
The molecular formula is X-C 6 H 4 -N-N-C 6 H 3 OH-Y, whereby said X is selected from alkanes, thereby imparting good oil solubility characteristics to the entire organic agent molecule. An oil-soluble organic reagent is mixed with the metal oxide nanoparticle sample to form an emulsion. X is further preferably selected from the group consisting of- (CH) 2 ) n -CH 3 Wherein n, m are in the rangeThe surrounding organic reagent has proper viscosity, and the subsequent reaction can be smoothly carried out in a liquid phase state.
In some embodiments, the formula is X-C 6 H 4 -N-N-C 6 H 3 OH-Y in the organic reagent, Y is selected from- (CH) 2 ) m -HS, X is selected from- (CH) 2 ) n -CH 3 Wherein the value of m is an integer from 1 to 18; the value of n is selected from integers of 1 to 18.
Preferably, the formula is X-C 6 H 4 -N-N-C 6 H 3 Organic reagent of OH-Y is selected from CH 3 -(CH 2 ) n C 6 H 4 -C 6 H 4 -N-N-C 6 H 3 OH-C 6 H 3 OH-(CH 2 ) m -HS, including in particular but not exclusively CH 3 -(CH 2 ) 7 -C 6 H 4 -N-N-C 6 H 3 OH-(CH 2 ) 7 -HS。
In the step S02, the organic reagent and the metal oxide nanoparticle sample are mixed in a liquid phase medium, so that the metal oxide nanoparticle sample and the organic reagent are uniformly mixed, and an emulsion of the organic reagent and the metal oxide nanoparticle sample is obtained.
In the embodiment of the invention, the liquid phase medium is used as a dispersion medium, and the metal oxide nanoparticle sample and the organic reagent are fully mixed, so that after the organic reagent is dissociated into organic molecules, the organic molecules are uniformly reacted on the surface of the metal oxide nanoparticle sample, and the water-based metal oxide nanoparticles with uniformly distributed surface water-soluble ligands are obtained. In addition, the liquid phase medium also serves as a phase transfer reagent, and the reaction between the organic molecules dissociated from the organic reagent and the metal oxide nanoparticle sample is promoted.
The metal oxide nanoparticle sample is water-phase metal oxide nanoparticles, and correspondingly, the liquid-phase medium is a non-polar solvent. Preferably, the nonpolar solvent is at least one selected from toluene, chloroform, n-hexane, octane and carbon tetrachloride.
In some embodiments, the step of mixing the organic reagent and the metal oxide nanoparticle sample in a liquid phase medium comprises: dissolving the organic reagent in the liquid phase medium to form an organic solution; and mixing the organic solution and the metal oxide nanoparticle sample.
Preferably, the concentration of the organic reagent in the organic reagent solution is 0.1 to 10mmol/L. The concentration of the organic agent is related to the molecular weight of the organic agents listed above. When the molecular weight of the organic reagent is smaller, the concentration of the organic reagent is higher, so that the content of organic molecules dissociated by the organic reagent is higher, the organic molecules can be uniformly and fully distributed around the surface of the metal oxide nanoparticle sample, and the metal on the surface of the metal oxide nanoparticle sample can be effectively combined. When the molecular weight of the organic reagent is larger, the molecular weight of the dissociated corresponding organic molecule is also larger, and at this time, if the content is too high, the combination of the dissociated organic molecule and the metal oxide nanoparticle sample is not facilitated due to too large steric hindrance.
In the embodiment of the present invention, in the step of mixing the organic reagent and the metal oxide nanoparticle sample in a liquid phase medium, the molar mass ratio of the organic reagent to the metal oxide nanoparticles is (1 to 50 mmol): 100mg of the organic reagent and the metal oxide nanoparticle sample. If the content of the organic reagent is too low, the content of polar molecules dissociated from the organic reagent is low, which is not enough to fully convert the oil-phase metal oxide nanoparticles into the aqueous metal oxide nanoparticles. If the content of the organic reagent is too low, H dissociated from the organic reagent 2 N-C 6 H 3 The content of OH-Y molecules is low, and the electron-withdrawing groups on the surface of the metal oxide nano particles are not enough to effectively improve the electron transmission performance of the metal oxide nano particles. If the content of the organic reagent is too high, the organic reagent remains after the reduction reaction, and the remaining organic molecules are introduced into the metal oxide as impuritiesIn nanoparticles, the properties of metal oxide nanoparticles are affected. In particular, when metal oxide nanoparticles are used as an electron transport layer material in a light emitting device, since the remaining organic agent is an insulating molecule and does not conduct electricity, the electron transport efficiency of the resulting electron transport layer may be reduced.
In the embodiment of the present invention, the mixing treatment of the organic reagent and the metal oxide nanoparticle sample in the liquid phase medium is preferably performed at 20 to 60 ℃. Further, the gas atmosphere in which the organic reagent and the metal oxide nanoparticle sample are mixed in the liquid medium is preferably an inert gas atmosphere to prevent the introduction of an oxidizing gas from interfering with the reduction reaction in the following steps.
In step S03, an inorganic salt reducing agent is added to the emulsion for reacting with the organic reagent X-C 6 H 4 -N-N-C 6 H 3 The azide bond in OH-Y reacts, reducing it to an amino group and, finally, X-C 6 H 4 -N-N-C 6 H 3 Reductive dissociation of OH-Y into organic molecules X-C 6 H 4 -NH 2 And H 2 N-C 6 H 3 OH-Y. Dissociated H 2 N-C 6 H 3 OH-Y contains sulfydryl and tends to be combined with metal on the surface of a metal oxide nanoparticle sample, so that hydroxyl and phenyl with strong electron withdrawing performance are introduced on the surface of the metal oxide nanoparticle, and the electron transmission performance of the metal oxide nanoparticle is improved.
In a preferred embodiment, the inorganic salt reducing agent is selected from Na 2 S 2 O 4 、K 2 S 2 O 4 、MgS 2 O 4 、CaS 2 O 4 At least one of (1). Preferred embodiments, the X-C can be realized 6 H 4 -N-N-C 6 H 3 Reduction of the azido bond in OH-Y without affecting the properties of the phenyl and phenolic hydroxyl groups.
In a preferred embodiment, in the step of adding the inorganic salt reducing agent to the emulsion, the molar amount of the inorganic salt reducing agent to the organic reagent is (1-3): 1, adding an inorganic salt reducing agent to the emulsion. This can promote the rapid progress of the reduction reaction.
In the embodiment of the invention, the inorganic salt reducing agent is added into the emulsion in one step or slowly added, such as dropwise. The addition of the inorganic salt reducing agent to the emulsion is preferably carried out at 20 to 60 ℃. Further, the atmosphere in which the inorganic salt reducing agent is added to the emulsion is preferably an inert atmosphere to prevent the introduction of oxidizing gases that interfere with the reduction reaction.
In the embodiment of the invention, the method for adding the inorganic salt reducing agent into the emulsion comprises the following steps: and adding an inorganic salt reducing agent into the emulsion under the stirring condition in an inert atmosphere to promote the reduction reaction and the phase transition reaction, wherein the stirring time is 10-120 min. Adding an inorganic salt reducing agent into the emulsion, and phase separation exists during stirring until the metal oxide nanoparticles are completely dissolved. At this time, the produced aqueous phase metal oxide nanoparticles are dispersed in a polar liquid phase medium.
The mixed solution is treated by an inorganic salt reducing agent to obtain water-phase metal oxide nano particles with benzene rings and hydroxyl groups on the surface, and the layering phenomenon occurs. Further, a precipitant is added to the mixed system, and the water-phase metal oxide nanoparticles in the reaction system are precipitated and collected by centrifugal separation. Preferably, the precipitant is selected from at least one of ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl formate, methyl formate, propyl formate, and butyl formate, but is not limited thereto. Further preferably, in the step of adding the precipitant into the mixed system, the volume ratio of the precipitant to the mixed system is (1-5): 1, adding a precipitant to the mixed system to promote precipitation of the aqueous phase metal oxide nanoparticles. Further, separating out the water-phase metal oxide nanoparticles by adopting a high-speed centrifugation mode.
In a second aspect of embodiments of the present invention, there is provided a metal oxide nanoparticle prepared by the above method.
The metal oxide nanoparticles provided by the embodiment of the invention have excellent electron transmission efficiency because the surfaces of the particles contain electron-withdrawing benzene rings and hydroxyl groups.
The invention provides a quantum dot light-emitting diode, which comprises a cathode and an anode which are oppositely arranged, a quantum dot light-emitting layer arranged on the cathode and the anode, and an electron transmission layer arranged between the cathode and the quantum dot light-emitting layer, wherein part or all of the material of the electron transmission layer is the metal oxide nanoparticles prepared by the method or the metal oxide nanoparticles.
According to the quantum dot light-emitting diode provided by the embodiment of the invention, as the electron transport layer material contains or completely contains the metal oxide nanoparticles, the charge injection balance can be obviously improved, and the light-emitting efficiency and the service life of the quantum dot light-emitting diode are improved.
In some embodiments, the material of the electron transport layer is all the metal oxide nanoparticles prepared by the above method or the above metal oxide nanoparticles, thereby exerting the optimal performance of the metal oxide nanoparticles.
In some embodiments, the material of the electron transport layer includes the metal oxide nanoparticles prepared by the above method or the above metal oxide nanoparticles, and also includes other conventional electron transport materials, and the content of the conventional electron transport materials is not strictly limited. When the content of the metal oxide nanoparticles in the electron transport layer is higher, the charge injection balance is improved, and the effect of improving the luminous efficiency and the service life of the quantum dot light-emitting diode is more obvious.
The following description will be given with reference to specific examples.
Example 1
A preparation method of water-phase ZnO nanoparticles comprises the following steps:
taking 10mmol of organic reagent CH 3 -(CH 2 ) 8 -C 6 H 4 -N-N-C 6 H 3 OH-CH 2 Dispersing and fully dissolving the HS in 5ml of n-hexane reagent, then adding the organic reagent solution into 3ml of n-hexane solution containing 100mg of oil-soluble CdSe/ZnS red quantum dots, and mixing and stirring for 10min to form a homogeneous emulsion.
Taking Na containing 10mmol 2 S 2 O 4 Adding 10ml of aqueous solution into the emulsion at one time, stirring the mixed solution at room temperature under inert gas until the ZnO nanoparticles are dispersed in the polar reagent, and preparing the water-phase ZnO nanoparticles with benzene rings and hydroxyl groups on the surfaces.
Adding 15ml of ethyl acetate solution into the mixed system, and then separating by adopting a centrifugal separation mode to prepare the water-phase ZnO nanoparticles with the benzene rings and the hydroxyl groups on the surfaces.
Example 2
A quantum dot light emitting diode comprises a cathode and an anode which are oppositely arranged, a quantum dot light emitting layer arranged on the cathode and the anode, an electron transport layer arranged between the cathode and the quantum dot light emitting layer, and a hole transport layer arranged between the anode and the quantum dot light emitting layer, wherein the electron transport layer is made of the metal oxide nanoparticles prepared in the embodiment 1.
Comparative example 1
A quantum dot light emitting diode, which is different from example 2 in that the material of the electron transport layer is the ZnO nanoparticle sample provided in example 1.
Film mobility of the electron transport layers of the quantum dot light emitting diodes obtained in example 1 and comparative example, and solution dispersibility/haze values of the ZnO nanoparticle solution provided in example 1 and the ZnO nanoparticle sample solution provided in comparative example 1 were tested, and the results are shown in table 1 below.
TABLE 1
As can be seen from table 1, compared to comparative example 1, the ZnO nanoparticle solution obtained by the method for preparing ZnO nanoparticles provided in the embodiment of the present invention has better dispersibility; the film mobility of the quantum dot light-emitting diode obtained by the method is improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (12)
1. A method for preparing metal oxide nanoparticles, comprising the steps of:
providing a compound of formula X-C 6 H 4 -N-N-C 6 H 3 An organic reagent of OH-Y and a metal oxide nanoparticle sample to be treated; X-C 6 H 4 -N-N-C 6 H 3 In OH-Y, X is alkane, and Y is selected from hydrocarbon group containing at least one sulfhydryl group; wherein the metal oxide nanoparticle sample is selected from ZnO, niO, W 2 O 3 、Mo 2 O 3 、TiO 2 、SnO、ZrO 2 、Ta 2 O 3 At least one of;
and mixing the organic reagent and the metal oxide nanoparticle sample in a liquid phase medium, and adding an inorganic salt reducing agent to prepare the metal oxide nanoparticle.
2. The method of claim 1, wherein the metal oxide nanoparticles have the formula X-C 6 H 4 -N-N-C 6 H 3 OH-Y in the organic reagent, Y is selected from- (CH) 2 ) m -HS, wherein m is selected from integers from 1 to 18; and/or
The molecular formula is X-C 6 H 4 -N-N-C 6 H 3 OH-Y in the organic reagent, X is selected from- (CH) 2 ) n -CH 3 Wherein the value of n is selected from an integer of 1 to 18.
3. The method of claim 1, wherein the sample of metal oxide nanoparticles is aqueous phase metal oxide nanoparticles and the liquid phase medium is a non-polar solvent.
4. The method of claim 3, wherein the non-polar solvent is at least one selected from the group consisting of toluene, chloroform, n-hexane, octane, and carbon tetrachloride.
5. The method of any one of claims 1 to 4, wherein the inorganic salt reducing agent is selected from Na 2 S 2 O 4 、K 2 S 2 O 4 、MgS 2 O 4 、CaS 2 O 4 At least one of (1).
6. The method for producing metal oxide nanoparticles according to any one of claims 1 to 4, wherein the step of subjecting the sample of metal oxide nanoparticles and the organic reagent to a mixing treatment in a liquid-phase medium comprises: dissolving the organic reagent in the liquid phase medium to form an organic solution; and mixing the organic solution and the metal oxide nanoparticle sample.
7. The method for preparing metal oxide nanoparticles according to claim 6, wherein the concentration of the organic reagent in the organic solution is 0.1 to 10mmol/L.
8. The method for producing metal oxide nanoparticles according to any one of claims 1 to 4 and 7, wherein in the step of subjecting the sample of the metal oxide nanoparticles and the organic reagent to a mixing treatment in a liquid-phase medium, the ratio of the molar mass of the organic reagent to the molar mass of the metal oxide nanoparticles is (1 to 50 mmol): mixing the organic reagent and the metal oxide nanoparticle sample at a ratio of 100 mg.
9. The method of producing metal oxide nanoparticles of any one of claims 1 to 4 and 7, further comprising: adding a precipitant into the mixed system, and centrifugally separating and collecting.
10. The method of preparing metal oxide nanoparticles of claim 9, wherein the precipitating agent is selected from at least one of ethyl acetate, methyl acetate, propyl acetate, butyl acetate, ethyl formate, methyl formate, propyl formate, butyl formate; and/or
In the step of adding a precipitant into the obtained mixed system, according to the volume ratio of the precipitant to the mixed system being (1-5): 1, adding a precipitant into the mixed system.
11. A metal oxide nanoparticle, wherein the metal oxide nanoparticle is prepared by the method of any one of claims 1 to 10.
12. A quantum dot light-emitting diode comprising a cathode and an anode which are oppositely arranged, a quantum dot light-emitting layer arranged between the cathode and the anode, and an electron transport layer arranged between the cathode and the quantum dot light-emitting layer, wherein the material of the electron transport layer is partially or totally the metal oxide nanoparticles prepared by the method of any one of claims 1 to 10 or the metal oxide nanoparticles of claim 11.
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| US20040248282A1 (en) * | 2001-06-11 | 2004-12-09 | Pisharody Sobha M. | Electronic detection of biological molecules using thin layers |
| CN101124156A (en) * | 2004-05-19 | 2008-02-13 | 得克萨斯A&M大学体系 | Process for preparing nano-sized metal oxide particles |
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| US20040248282A1 (en) * | 2001-06-11 | 2004-12-09 | Pisharody Sobha M. | Electronic detection of biological molecules using thin layers |
| CN101124156A (en) * | 2004-05-19 | 2008-02-13 | 得克萨斯A&M大学体系 | Process for preparing nano-sized metal oxide particles |
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