CN101413141A - Method for growing ZnO nano-wire array on flexible substrate - Google Patents

Abstract

Translated fromChinese

本发明公开的柔性衬底上生长ZnO纳米线阵列的方法，步骤包括：将清洗过的柔性衬底放入脉冲激光沉积装置生长室中，以ZnO陶瓷为靶材，生长室通入O₂气体，控制压强为0.01～2Pa，室温下在柔性衬底上脉冲激光沉积ZnO籽晶层；分别配置浓度为0.01～0.1mol/L的硝酸锌水溶液和六次甲基四胺水溶液，并按体积比1∶1混合，再将沉积有ZnO籽晶层的柔性衬底浸没于混合溶液中，在70～100℃下反应1～12h后取出，用去离子水漂洗，烘干，即可。本发明方法所用设备简单，易操作，制备的ZnO纳米线阵列化良好，粗细均匀，成本低，适宜于大规模生产。The method for growing a ZnO nanowire array on a flexible substrate disclosed by the invention, the steps include: putting the cleaned flexible substrate into a growth chamber of a pulsed laser deposition device, using ZnO ceramics as a target, and feeding_O2 gas into the growth chamber , control the pressure at 0.01-2Pa, pulse laser deposit the ZnO seed crystal layer on the flexible substrate at room temperature; configure zinc nitrate aqueous solution and hexamethylenetetramine aqueous solution with the concentration of 0.01-0.1mol/L respectively, and according to the volume ratio 1:1 mixing, then immersing the flexible substrate deposited with the ZnO seed layer in the mixed solution, reacting at 70-100° C. for 1-12 hours, taking it out, rinsing with deionized water, and drying. The equipment used in the method of the invention is simple and easy to operate, and the prepared ZnO nanowires are well arrayed, uniform in thickness and low in cost, and are suitable for large-scale production.

Description

Translated fromChinese

柔性衬底上生长ZnO纳米线阵列的方法Method for growing ZnO nanowire array on flexible substrate

技术领域technical field

本发明涉及ZnO纳米线阵列的生长方法，尤其是柔性衬底上生长ZnO纳米线阵列的方法。The invention relates to a method for growing a ZnO nanowire array, in particular to a method for growing a ZnO nanowire array on a flexible substrate.

背景技术Background technique

ZnO是一种宽禁带化合物半导体材料，室温下的禁带宽度为3.37eV，激子束缚能高达60meV，其激子能够在室温及以上温度下稳定存在，是制备半导体激光器(LDs)、发光二极管(LEDs)的理想材料。ZnO还是现今发现的微纳米结构最为丰富的材料，ZnO的纳米结构在制备纳米光电子器件和纳米电子器件方面有很好的应用价值，另外，ZnO的纳米结构还可以在场发射、医疗、生物传感等领域得到应用。ZnO is a wide bandgap compound semiconductor material. The bandgap width at room temperature is 3.37eV, and the exciton binding energy is as high as 60meV. Its excitons can exist stably at room temperature and above. Ideal material for diodes (LEDs). ZnO is also the material with the most abundant micro-nano structure found today. The nano-structure of ZnO has good application value in the preparation of nano-optoelectronic devices and nano-electronic devices. In addition, the nano-structure of ZnO can also be used in field emission, medical treatment, and biosensing. and other fields have been applied.

聚对苯二甲酸乙二醇酯(PET)是热塑性聚酯中最主要的品种，具有耐蠕变、抗疲劳性、耐摩擦和尺寸稳定性好，磨耗小而硬度高，具有热塑性塑料中最大的韧性，电绝缘性能好，受温度影响小等特点。在PET上生长的ZnO纳米线阵列结合了柔性衬底的韧性和ZnO纳米线阵列导电性的优点，衬底和ZnO纳米线结合紧密，使其在触摸屏工业领域有良好的应用前景。用PET代替电阻式触摸屏的有机玻璃，ZnO纳米线膜代替ITO薄膜，解决了触摸屏工作面和导电涂层结合不紧密的问题，而且以纳米线阵列作为电极接触点可以使灵敏度大大提高。Polyethylene terephthalate (PET) is the most important variety of thermoplastic polyesters. It has creep resistance, fatigue resistance, friction resistance, good dimensional stability, low wear and high hardness, and has the largest Excellent toughness, good electrical insulation performance, and little influence by temperature. The ZnO nanowire array grown on PET combines the toughness of the flexible substrate and the advantages of the conductivity of the ZnO nanowire array. The substrate and the ZnO nanowire array are closely combined, making it have a good application prospect in the touch screen industry. Replacing the plexiglass of the resistive touch screen with PET, and replacing the ITO film with ZnO nanowire film solves the problem of loose bonding between the working surface of the touch screen and the conductive coating, and the sensitivity can be greatly improved by using the nanowire array as the electrode contact point.

目前，氧化锌纳米线(棒)的制备方法主要有：金属有机气相外延生长(MOVPE)、化学气相沉积法(CVD)、脉冲激光沉积(PLD)、电化学气相沉积、模板法和水热法等等，但均处于研究探索阶段，还不能形成规模生产。同时如MOVPE、CVD、PLD、水热法等方法需要昂贵的仪器设备和苛刻的工艺条件。At present, the preparation methods of zinc oxide nanowires (rods) mainly include metal organic vapor phase epitaxy (MOVPE), chemical vapor deposition (CVD), pulsed laser deposition (PLD), electrochemical vapor deposition, template method and hydrothermal method. etc., but they are all in the stage of research and exploration, and cannot be mass-produced yet. At the same time, methods such as MOVPE, CVD, PLD, and hydrothermal methods require expensive equipment and harsh process conditions.

发明内容Contents of the invention

本发明的目的是提供一种设备、工艺简单，成本低，易操作的在柔性衬底上生长ZnO纳米线阵列的方法。The purpose of the present invention is to provide a method for growing ZnO nanowire array on a flexible substrate with simple equipment and process, low cost and easy operation.

本发明的在柔性衬底上生长ZnO纳米线阵列的方法，包括以下步骤：The method for growing a ZnO nanowire array on a flexible substrate of the present invention comprises the following steps:

1)分别配置浓度为0.01～0.1mol/L的硝酸锌水溶液和浓度为0.01～0.1mol/L的六次甲基四胺水溶液；1) An aqueous solution of zinc nitrate with a concentration of 0.01 to 0.1 mol/L and an aqueous solution of hexamethylenetetramine with a concentration of 0.01 to 0.1 mol/L are prepared respectively;

2)将清洗过的柔性衬底放入脉冲激光沉积装置生长室中，以ZnO陶瓷为靶材，靶材与衬底之间的距离保持为4～6cm，生长室真空度至少抽至10^-3Pa，生长室通入O₂气体，控制压强为0.01～2Pa，室温下在柔性衬底上脉冲激光沉积ZnO籽晶层；2) Put the cleaned flexible substrate into the growth chamber of the pulsed laser deposition device, use ZnO ceramics as the target material, keep the distance between the target material and the substrate at 4-6 cm, and pump the vacuum degree of the growth chamber to at least 10^{- 3} Pa, the growth chamber is fed with O₂ gas, the pressure is controlled at 0.01-2 Pa, and the ZnO seed layer is deposited on the flexible substrate by pulse laser at room temperature;

3)将硝酸锌水溶液和六次甲基四胺水溶液按体积比1：1混合，再将上述沉积有ZnO籽晶层的柔性衬底浸没于混合溶液中，在70～100℃下反应1～12h后取出，用去离子水漂洗，烘干，即可。3) Mix the zinc nitrate aqueous solution and the hexamethylenetetramine aqueous solution at a volume ratio of 1:1, then immerse the flexible substrate deposited with the ZnO seed layer in the mixed solution, and react at 70-100°C for 1- Take it out after 12 hours, rinse it with deionized water, and dry it.

上述的柔性衬底可以是聚对苯二甲酸乙二醇酯(PET)、聚酰亚胺(PI)聚苯并咪唑(PBD)，聚苯并恶唑(PBO)、聚乙烯(PE)、聚丙烯(PP)、聚苯乙烯(PS)或聚对萘二甲酸乙二醇酯(PEN)。The above flexible substrate can be polyethylene terephthalate (PET), polyimide (PI) polybenzimidazole (PBD), polybenzoxazole (PBO), polyethylene (PE), Polypropylene (PP), polystyrene (PS) or polyethylene naphthalate (PEN).

生长的ZnO纳米线的长度可以通过调节浸没于混合溶液中的时间来控制。The length of the grown ZnO nanowires can be controlled by adjusting the time of immersion in the mixed solution.

通常，脉冲激光沉积的激光功率为150～300mJ，激光重复频率3Hz。Usually, the laser power of pulsed laser deposition is 150-300mJ, and the laser repetition frequency is 3Hz.

本发明的有益效果在于：The beneficial effects of the present invention are:

1)本发明方法所用设备简单，易操作，成本低，适宜于大规模生产。1) The equipment used in the method of the present invention is simple, easy to operate, low in cost, and suitable for large-scale production.

2)制备的ZnO纳米线阵列化良好，粗细均匀，结合了柔性衬底和ZnO纳米线阵列的优点，在触摸屏领域有广阔的应用前景。2) The prepared ZnO nanowires are well arrayed and uniform in thickness, combining the advantages of flexible substrates and ZnO nanowire arrays, and have broad application prospects in the field of touch screens.

附图说明Description of drawings

图1是ZnO纳米线阵列的SEM图。Figure 1 is a SEM image of a ZnO nanowire array.

具体实施方式Detailed ways

以下结合实例对本发明作进一步的说明。Below in conjunction with example the present invention will be further described.

实施例1Example 1

1)分别配置浓度为0.05mol/L的硝酸锌水溶液和浓度为0.05mol/L的六次甲基四胺水溶液；1) a zinc nitrate aqueous solution with a concentration of 0.05mol/L and a hexamethylenetetramine aqueous solution with a concentration of 0.05mol/L are respectively configured;

2)将清洗过的PET衬底放入脉冲激光沉积装置生长室中，以ZnO陶瓷为靶材，靶材与衬底之间的距离保持为4.5cm，生长室真空度至少抽至10^-3Pa，生长室通入O₂气体，控制压强为0.03Pa，激光功率为210mJ，激光重复频率3Hz，室温下在PET衬底上沉积2min，得到ZnO籽晶层；2) Put the cleaned PET substrate into the growth chamber of the pulsed laser deposition device, use ZnO ceramics as the target material, keep the distance between the target material and the substrate at 4.5 cm, and pump the vacuum degree of the growth chamber to at least 10^-3 Pa, the growth chamber is fed with_O2 gas, the control pressure is 0.03Pa, the laser power is 210mJ, the laser repetition frequency is 3Hz, and deposited on the PET substrate for 2min at room temperature to obtain the ZnO seed layer;

3)将硝酸锌水溶液和六次甲基四胺水溶液按体积比1：1混合，再将上述沉积有ZnO籽晶层的柔性衬底浸没于混合溶液中，在90℃下反应6h后取出，用去离子水反复漂洗，烘干，制得ZnO纳米线阵列。3) Mix the zinc nitrate aqueous solution and the hexamethylenetetramine aqueous solution at a volume ratio of 1:1, then immerse the flexible substrate deposited with the ZnO seed layer in the mixed solution, react at 90°C for 6 hours, and take it out. Rinse and dry repeatedly with deionized water to prepare ZnO nanowire arrays.

ZnO纳米线阵列如图1所示，平均直径为0.8μm，ZnO纳米线的长度为600nm。The ZnO nanowire array is shown in Figure 1, with an average diameter of 0.8 μm and a length of ZnO nanowires of 600 nm.

实施例2Example 2

1)分别配置浓度为0.01mol/L的硝酸锌水溶液和浓度为0.01mol/L的六次甲基四胺水溶液；1) a zinc nitrate aqueous solution with a concentration of 0.01mol/L and a hexamethylenetetramine aqueous solution with a concentration of 0.01mol/L are respectively configured;

2)将清洗过的PET衬底放入脉冲激光沉积装置生长室中，以ZnO陶瓷为靶材，靶材与衬底之间的距离保持为6cm，生长室真空度至少抽至10^-3Pa，生长室通入O₂气体，控制压强为0.02Pa，激光功率为150mJ，激光重复频率3Hz，室温下在PET衬底上沉积5min，得到ZnO籽晶层；2) Put the cleaned PET substrate into the growth chamber of the pulsed laser deposition device, use ZnO ceramics as the target material, keep the distance between the target material and the substrate at 6 cm, and pump the vacuum degree of the growth chamber to at least 10^-3 Pa , the growth chamber is fed with_O2 gas, the control pressure is 0.02Pa, the laser power is 150mJ, the laser repetition frequency is 3Hz, and the ZnO seed layer is obtained on the PET substrate at room temperature for 5min;

3)将硝酸锌水溶液和六次甲基四胺水溶液按体积比1：1混合，再将上述沉积有ZnO籽晶层的柔性衬底浸没于混合溶液中，在100℃下反应1h后取出，用去离子水反复漂洗，烘干，制得粗细均匀、长度为200nm的ZnO纳米线阵列。3) Mix the zinc nitrate aqueous solution and the hexamethylenetetramine aqueous solution at a volume ratio of 1:1, then immerse the flexible substrate deposited with the ZnO seed layer in the mixed solution, react at 100°C for 1 hour, and then take it out. Repeatedly rinsing with deionized water and drying to prepare a ZnO nanowire array with a uniform thickness and a length of 200 nm.

实施例3Example 3

1)分别配置浓度为0.1mol/L的硝酸锌水溶液和浓度为0.1mol/L的六次甲基四胺水溶液；1) a zinc nitrate aqueous solution with a concentration of 0.1mol/L and a hexamethylenetetramine aqueous solution with a concentration of 0.1mol/L are respectively configured;

2)将清洗过的PI衬底放入脉冲激光沉积装置生长室中，以ZnO陶瓷为靶材，靶材与衬底之间的距离保持为6cm，生长室真空度至少抽至10^-3Pa，生长室通入O₂气体，控制压强为0.2Pa，激光功率为300mJ，激光重复频率3Hz，室温下在PI衬底上沉积2min，得到ZnO籽晶层；2) Put the cleaned PI substrate into the growth chamber of the pulsed laser deposition device, use ZnO ceramics as the target material, keep the distance between the target material and the substrate at 6 cm, and pump the vacuum degree of the growth chamber to at least 10^-3 Pa , the growth chamber is fed with_O2 gas, the control pressure is 0.2Pa, the laser power is 300mJ, the laser repetition frequency is 3Hz, and the ZnO seed layer is obtained on the PI substrate at room temperature for 2min;

3)将硝酸锌水溶液和六次甲基四胺水溶液按1：1的体积比混合，再将上述沉积有ZnO籽晶层的PI衬底浸没于混合溶液中，在70℃下反应12h后取出，用去离子水反复漂洗，烘干，制得粗细均匀、长度为1μm的ZnO纳米线阵列。3) Mix the zinc nitrate aqueous solution and the hexamethylenetetramine aqueous solution at a volume ratio of 1:1, then immerse the PI substrate deposited with the ZnO seed layer in the mixed solution, react at 70°C for 12h, and then take it out , rinsed repeatedly with deionized water, and dried to prepare a ZnO nanowire array with uniform thickness and a length of 1 μm.

Claims (3)

1. The method of 1 growing ZnO nano-wire array on flexible substrate may further comprise the steps:

   1) configuration concentration is the zinc nitrate aqueous solution of 0.01～0.1mol/L and the hexamethylenetetramine aqueous solution that concentration is 0.01～0.1mol/L respectively;

   2) washed flexible substrate being put into pulsed laser deposition device growth room, is target with the ZnO pottery, and the distance between target and the substrate remains 4～6cm, and growth room's vacuum tightness is evacuated to 10 at least^-3Pa, the growth room feeds O₂Gas, control pressure is 0.01～2Pa, under the room temperature on flexible substrate pulsed laser deposition ZnO inculating crystal layer;

   3) with zinc nitrate aqueous solution and the 1:1 mixing by volume of the hexamethylenetetramine aqueous solution, the flexible substrate with the above-mentioned ZnO of depositing inculating crystal layer is immersed in the mixing solutions again, takes out behind reaction 1～12h down at 70～100 ℃, uses rinsed with deionized water, and oven dry gets final product.
2. 2. the method for growing ZnO nano-wire array on flexible substrate according to claim 1, it is characterized in that said flexible substrate is polyethylene terephthalate, polyimide, polybenzimidazole, polybenzoxazoles, polyethylene, polypropylene, polystyrene or poly-to (ethylene naphthalate).
3. 3. the method for growing ZnO nano-wire array on flexible substrate according to claim 1, the laser power that it is characterized in that pulsed laser deposition is 150～300mJ, laser repetition rate 3Hz.

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