CN103241764B - Preparation method of three-dimensional zinc oxide flower-like structure - Google Patents

Abstract

The invention relates to a preparation method of a three-dimensional zinc oxide flower-like structure. The preparation method comprises the steps of preparing a zinc oxide induction layer substrate, preparing a precursor of a zinc oxide flower-like structure and calcining, thus the zinc oxide flower-like structure product is obtained. The three-dimensional zinc oxide flower-like multilevel structure prepared by the invention is formed by self assembly of zinc oxide nanosheets. The preparation method of the three-dimensional zinc oxide flower-like structure has the characteristics of simple process, easiness for operation, no specific reaction container, environmental friendliness, high repeatability and applicability to preparation on a large scale.

Description

The preparation method of three-dimensional zinc oxide flower-like structure

Technical field

The invention belongs to Nano/micron material, particularly a kind of preparation method of three-dimensional zinc oxide flower-like structure, this synthetic method craft is simple, easy to operate without the need to special reaction container, environmentally friendly, and repeatability is high, is applicable to preparation in enormous quantities.

Background technology

Zinc oxide (ZnO) is as the direct semiconductor material with wide forbidden band of a kind of novel II-VI group, there is the multiple performances such as piezoelectricity, thermoelectricity, air-sensitive, photoconduction, at room temperature, its energy gap is 3.37eV, there is higher exciton bind energy (60meV simultaneously, be greater than the heat energy 26meV under room temperature), be widely used in photoelectric field.The character of zinc oxide depends on its profile to a great extent, in recent years, and the zinc oxide of the various pattern that utilized different methods to prepare, as bar-shaped in one-dimentional structure (X.Z.Zhang, X.J.Zhang, J.B.Xu, X.D.Shan, J.Xu, and D.P.Yu Opt.Lett.2009,34,2533-2535), tubulose (H.X.Dong, Z.H.Chen, L.X.Sun, W.Xie, J.Mater.Chem.2010,20,5510-5515); Two-dirnentional structure band shape (X.L.Xu, Frederic S.F.Brossard, David A.Williams, Appl.Phys.Lett.2009,94,231103); Three-dimensional structure flower-shaped (Q.Hou etal./Electrochimica Acta 78 (2012) 55 – 64) etc.Wherein three-dimensional flower-shaped multilevel hierarchy is owing to having larger specific surface area, showing special advantage and huge application prospect in the field such as efficient, miniature gas-sensitive sensor, photocatalyst and enjoy people to pay close attention to, is one of the focus in micro-nano preparation research field in recent years.

Conventional synthetic method for three-dimensional flower-shaped ZnO multi-level nano-structure mainly contains hydrothermal method (Naoyuki Ueno, Akinobu Yamamoto, Yoshiaki Uchida, Yasuyuki Egashira, Norikazu Nishiyama, MaterialsLetters 86 (2012) 65 – 68), chemical baths (Huihu Wang, Changsheng Xie, Journal of CrystalGrowth 291 (2006) 187 – 195), electroplating deposition method (Qin Hou, Liqun Zhu, Haining Chen, Huicong Liu, Weiping Li, Electrochimica Acta 78 (2012) 55 – 64) etc.Wherein, water heat transfer technology needs high temperature and high pressure environment, and influence factor is more, and Material growth efficiency is lower; Although chemical baths relatively hydrothermal method preparation process is simple, need in Material growth process to add other solution, very easily introduce impurity, product controllability is poor; Electroplating deposition method process is complicated, is difficult to be applied to industrial production.Preparation method provided by the invention avoids above-described deficiency, does not need specific reaction vessel, and the method just by simple, economy, environmental protection under normal pressure, low temperature successfully prepares the flower-shaped multilevel hierarchy of three-dimensional zinc oxide, and productive rate is high, process control.

Summary of the invention

The invention provides the preparation method of the flower-shaped multilevel hierarchy of a kind of three-dimensional zinc oxide.The method obtains the flower-shaped multilevel hierarchy be made up of Zinc oxide nano sheet, and flower-like structure size is about 3 ~ 5 μm.This synthetic method has the advantages that technique is simple, easy to operate, environmentally friendly and repeatability is high.

The technology of the present invention solution is as follows:

A preparation method for three-dimensional zinc oxide flower-like structure, its feature is that the method comprises the following steps:

1. compound concentration is the zinc nitrate aqueous solution of 0.1mol/L, this solution is dropped in the substrate surface of Material growth, after drying, in 500 DEG C of calcining 30min, obtains the substrate being covered with inducing zinc layer growth;

2. had by substrate one of inducing layer to face up and put into culture dish, add zinc acetate aqueous solution until flood substrate, at least 8 hours are left standstill in the temperature condition of 5 ~ 70 DEG C, react rear taking-up substrate, with distilled water cleaning 2 ~ 3 times, then the baking oven putting into 50 DEG C is dry, obtains the presoma of zinc oxide flower-like structure;

3. by calcining under the temperature condition of described zinc oxide precursor more than 150 DEG C 24 hours, the zinc oxide of three-dimensional flower-shaped structure is obtained.

Described growth substrates material is sheet glass, ceramic plate, silicon chip or quartz plate.

Described zinc acetate aqueous solution concentration is 0.01-0.2mol/L.

The three-dimensional zinc oxide structure of preparation is by the flower-like structure of a large amount of nanometer sheet self-assembly.

Accompanying drawing explanation

Fig. 1 is scanning electronic microscope (SEM) figure of the three-dimensional flower-shaped zinc oxide of the present invention;

Fig. 2 is that the transmission electricity of the three-dimensional flower-shaped zinc oxide of the present invention is at microscope (TEM) figure;

Fig. 3 is that the presoma of the three-dimensional flower-shaped zinc oxide of the present invention calcines X-ray diffraction (XRD) figure after 24 hours at temperature 200 DEG C.

Embodiment

In order to be described further the three-dimensional flower-shaped zinc oxide of preparation, the present embodiment is implemented according to technical solution of the present invention, provides concrete embodiment and flow process.

Embodiment 1

(1) take 0.30g zinc nitrate and be dissolved in 10ml deionized water, obtain the zinc nitrate aqueous solution of 0.1mol/L, monocrystalline silicon piece (10mm × 15mm) is used respectively deionized water and dehydrated alcohol ultrasonic cleaning 5min, drying, 0.1ml zinc nitrate aqueous solution is dropped on silicon chip, be placed on 50 DEG C of baking oven inner drying 60min, after drying completes, in 500 DEG C of calcining 30min, obtain the substrate being covered with Zinc oxide film.

(2) get 0.18g zinc acetate and be dissolved in 10ml deionized water, obtain the zinc acetate aqueous solution of 0.1mol/L, had by substrate one of Zinc oxide film to face up and put into culture dish, add the zinc acetate aqueous solution that configures until substrate is flooded completely, at 10 DEG C, leave standstill 24h, take out substrate, with distilled water cleaning 2-3 time, then put into the dry 30min of baking oven, obtain the presoma of flower-like structure zinc oxide;

(3) presoma obtained is put into retort furnace, be warming up to 200 DEG C with the speed of 2 DEG C/min, calcining 24h, treats that furnace temperature naturally cools to room temperature, takes out substrate, obtains three-dimensional flower-shaped zinc oxide.

The zinc oxide of three-dimensional flower-shaped structure that what the present embodiment obtained have carries out morphology observation and structural analysis by SEM, TEM, XRD, and related results asks for an interview Fig. 1, Fig. 2 and Fig. 3.

Embodiment 2

In the zinc oxide preparation process of the three-dimensional flower-shaped structure of the present embodiment paper examines, substrate material, the concentration of zinc acetate aqueous solution, soak time, soaking temperature, calcining temperature is on the impact of prepared zinc oxide pattern.Specific experiment process is with embodiment 1, and difference is, changes substrate material respectively, the concentration of zinc acetate aqueous solution, soak time, soaking temperature, calcining temperature, and concrete experiment parameter is as table 1.From experimental result, along with the reduction of zinc acetate concentration, oxidation zinc metal sheet is thinning, and flower-like structure space becomes large.Increase soak time not have much affect to pattern.Temperature of reaction exists, and when less than 70 DEG C, improves temperature and speed of response can be made to accelerate, can not obtain the zinc oxide of three-dimensional flower-shaped structure when temperature is greater than 70 DEG C.Calcining temperature needs more than 150 DEG C.

Above-mentioned three-dimensional flower-shaped zinc oxide experiment condition prepared by table 1:

Sequence number

Substrate

Zinc acetate concentration

Soak time

Soaking temperature

Calcining temperature

Change project

1

Monocrystalline silicon piece

0.1mol/L

24h

10℃

200℃

2

Sheet glass

0.1mol/L

24h

10℃

200℃

Base material

3

Ceramic plate

0.1mol/L

24h

10℃

200℃

Base material

4

Quartz plate

0.1mol/L

24h

10℃

200℃

Base material

6

Monocrystalline silicon piece

0.01mol/L

24h

10℃

200℃

Strength of solution

7

Monocrystalline silicon piece

0.1mol/L

24h

10℃

200℃

Strength of solution

8

Monocrystalline silicon piece

0.2mol/L

24h

10℃

200℃

Strength of solution

9

Monocrystalline silicon piece

0.1mol/L

8h

10℃

200℃

Soak time

10

Monocrystalline silicon piece

0.1mol/L

24h

10℃

200℃

Soak time

11

Monocrystalline silicon piece

0.1mol/L

48h

10℃

200℃

Soak time

12

Monocrystalline silicon piece

0.1mol/L

24h

5℃

200℃

Soaking temperature

13

Monocrystalline silicon piece

0.1mol/L

24h

30℃

200℃

Soaking temperature

14

Monocrystalline silicon piece

0.1mol/L

24h

70℃

200℃

Soaking temperature

15

Monocrystalline silicon piece

0.1mol/L

24h

10℃

150℃

Calcining temperature

16

Monocrystalline silicon piece

0.1mol/L

24h

10℃

200℃

Calcining temperature

17

Monocrystalline silicon piece

0.1mol/L

24h

10℃

400℃

Calcining temperature

Claims (3)

1. a preparation method for three-dimensional zinc oxide flower-like structure, is characterized in that this preparation method comprises the following steps:

1. compound concentration is the zinc nitrate aqueous solution of 0.1mol/L, this solution is dropped in the substrate surface of Material growth, after drying, in 500 DEG C of calcining 30min, obtains the substrate being covered with inducing zinc layer growth;

2. had by substrate one of inducing layer to face up and put into culture dish, add zinc acetate aqueous solution until flood substrate, at least 8 hours are left standstill in the temperature condition of 5 ~ 70 DEG C, react rear taking-up substrate, with distilled water cleaning 2 ~ 3 times, then the baking oven putting into 50 DEG C is dry, obtains the presoma of zinc oxide flower-like structure;

3. by calcining under the temperature condition of described zinc oxide precursor more than 150 DEG C 24 hours, the zinc oxide of three-dimensional flower-shaped structure is obtained.

2. in accordance with the method for claim 1, it is characterized in that growth substrates material is sheet glass, ceramic plate, silicon chip or quartz plate.

3. in accordance with the method for claim 1, it is characterized in that described zinc acetate aqueous solution concentration is 0.01-0.2mol/L.