TWI220539B - Manufacturing method of regularly arranged nanometer dot array - Google Patents

Abstract

The present invention provides a manufacturing method of regularly arranged nanometer dot array, which comprises: providing a substrate and forming a conductive layer on the substrate; next, forming a metal layer on the conductive layer; then performing an anode oxidization process step to oxidize the metal on the surface to form an oxidization template of nanometer hole array, continuing to perform the anode oxidization process step, and oxidizing the surface of the conductive layer via the oxidization template of nanometer hole array to form a metal oxidization nanometer dot array corresponding the nanometer hole array; and finally removing the oxidization template of the nanometer hole array to form a metal oxidization nanometer dot array.

Description

1220539 V. Description of the invention (l) The technical field to which the invention belongs ... The present invention relates to a method for making a nano-dot array =-a method for making a regular row by using anodizing technology: a temple is a method related to a rice-dot array. | Oxide Nanotechnology Prior technology: The most commonly used method for making semiconductor nano- dots Stranski-Krastanow growth mode (s —K m〇de). This system selects an appropriate substrate for heteroepitaxial growth. When the epitaxial = first method requires a large difference in lattice constants and the deposition exceeds a certain thickness 〃 2 the substrate can not withstand the strain, the epitaxial material will Ground self-aggregation forms nanometer-sized quantum dot structures due to sel f-assembly to reduce energy. However, the spatial arrangement-in-squareness distribution of quantum dots made in this way is uneven. In addition, Stranski-Krastan〇w growth mode ⑺K «lode) is only applicable to a few heteroepitaxial systems with high lattice strain, for example,

InAs QDs / GaAs sub ·, InAs QDs / InP sub ·, and Ge QDs / Si sub · and other systems. Until now, there has not been a high-efficiency and effective way to control the growth of quantum dots', thus limiting the applicability of quantum dot elements. In order to effectively control the growth of quantum dots, 1% polar oxidation of nano-holes with regular arrangement | Lu (anodic aluminum oxide (ΑΑ0) is often used as a template for child dots ^: dot material (^ emp 1 a ^ e). Porous anodized alumina can be obtained by placing pure ions in an electrolyte and applying an appropriate voltage for anodization. The formation mechanism of the pores is mainly the electric field assisting the competitive reaction between dissolved alumina and alumina production.

1220539 V. Description of the invention (2) Straight nano-holes developed under '2 The arrangement of pores is' and the depth of the pores is the highest comparable. Therefore, it has great oxidization conditions. The oxidation conditions can be refined. It is very suitable to use aluminum foil for anode The process of peeling the foil from the nano-holes in the selective process of the sink cannot cooperate. The rate of anodic oxidation and bathing on the substrate is equal to the pull rate, n, and when J is ten, a hole is formed? The diameter of the pores ranges from ten to several hundred nanometers. The densest packing arrangement of hexagons (heXag0nal) reaches several hundred microns, and it has a positive aspect ratio with the anodizing time. By changing the size of the nanopores, the anode controls the template for quantum dot growth. However, in general, the anodized aluminum must be lift-off, adsorbed on the substrate, and then accumulate neutrons. The efficiency of this method is low, and the current problem is solved. The present invention proposes to use aluminum film directly on aluminum to make it compatible with the current semiconductor thin film manufacturing process. SUMMARY OF THE INVENTION In view of this, the object of the present invention is to provide a nanometer dot. The manufacturing method of the array is to adjust the anode anodizing process conditions to control the size of the anodized pores, and then control the size of the nano dots, so as to achieve the production of regularly arranged nano dot arrays on any substrate. According to the above purpose, the present invention provides a method for manufacturing a regularly arranged nano-dot array, which includes the following steps: providing a substrate; forming a conductive layer on the substrate; forming a metal layer on the conductive layer; performing an anodizing step, The metal layer is oxidized on the surface to form a nano-scale hole array oxide template; the anode anodizing step is continuously performed, and the conductive layer surface is oxidized to form a nano-scale through the nano-scale hole array oxide template

1220539 V. Description of the invention (3)

Nanometer dot array 1 and nanometer removal According to the above purpose, the manufacturing method of the present invention includes the following steps on the above substrate; forming a conductive layer on the conductive layer; and performing anodizing treatment to form a nanometer-level hole array. Oxidation treatment step, through the surface oxidation of the nano-level hole layer to form nano-point hole nano-point array; remove the non-oxidized part of the nano-level holes, leaving the metal oxide oxide nano-point array as a mask, etch Point array. Provide a regularly arranged nano-matrix: provide a substrate; form a thin film on the thin film; form a metal layer in the step, and place a metal layer oxide template on the surface; continue to perform an anodic oxide array oxide template, and conduct a conductive array Corresponding oxide template and conductive layer nanometer dot array of a metal oxide array; and a metal etched film to convert the film to a nanometer

In the following, the drawings and preferred embodiments are described in more detail. Embodiments: Embodiment 1 The nano-dot array can be widely used in photovoltaic elements, gas sensors, photocatalysts, optical elements, magnetic recording media, and solar cells. The first embodiment of the present invention uses the regular arrangement of titanium oxide nano-dot arrays as an example to illustrate the present invention, but does not limit the present invention. FIG. 4 is a cross-sectional view showing the process of the regularly arranged titanium oxide nano-dot array according to the first embodiment of the present invention.凊 Refer to Figure 1 to provide a substrate 丨 〇 〇, such as silicon substrate, glass substrate

1220539 V. Description of the invention (5) 'Chromic acid 1.5 wt%, temperature 60 ° C, time 2 hours. According to a preferred embodiment of the present invention, the substrate 100 is placed in an electrolyte, such as oxalic acid (0.3 ~ 0.4M) or sulfuric acid (1.2M), and an appropriate voltage is applied, such as 40 volts (V). , Porous anodized alumina can be obtained by performing an anodizing reaction at room temperature, and the diameter is from 20 to 60 nanometers. The formation mechanism of the pores is mainly the competitive reaction between electric field-assisted dissolution of alumina and the formation of alumina '. When the rate of alumina generation and dissolution reaches equilibrium, a through-going nano-pore is formed. The arrangement of the holes is the closest packing of hexagonal, and the depth of the holes can be up to several hundred microns, which is proportional to the time of anodizing, so it has a great aspect ratio. Figure 5 It shows the relationship between current density and time (j — T) during anodization. Point A refers to the anode current density at the time of generation of the anodized inscription (a n o d ^ c a 1 u m i n u m ο X i de e, A AO). When the anodic aluminum oxide hole 4 2 develops to the interface between the metal shale layer 140 and the titanium nitride 120, the anode current density starts to decrease sharply (point B). Then the anodic oxidation reaction of titanium nitride 12 20 begins. (◦ point) 'forms a regular array of titanium oxide nano-point arrays 丨 2 2 and the final anode current is also reduced to the lowest value to represent the end of the anodization reaction (point D). The size of the regular array of titanium oxide nano dot arrays 丨 2 2 is similar to that of anodic aluminum oxide (AA0) holes 142, which can be effectively controlled by the anodic oxidation parameters. The results are shown in the table below.

1220539

Voltage electrolyte electrolyte temperature Nano point / pore diameter 40 V oxalic acid, 0.3M room temperature 60 nm 30 V monoacid, 0.4M 1 ～ 5〇C — —--- 40 nm 15 V hard acid: 1.2M 5 to ΙΟ. . 20 nm-: ---

Figures 6a and 6b are SEM images of the aluminum / titanium nitride double-layered film after anodizing. The second image shows the top-view SEM image of the anodized aluminum nanopores, and the sixth image shows the anodized aluminum nanocrystals. SEM photograph of a section of a meter hole. As shown in Figure 6a, the self-assembled anodized aluminum pores have excellent uniformity of hole size distribution (~ 60nm) and regular arrangement. The nano-holes in the same area (domai η) are nearly perfect hexagonal arrangements. The size of the domain (domai η) grows as the time of the anodizing treatment increases. Figure 7a is a TEM image showing the bottom of the anodized aluminum hole and the titanium nitride interface. Figure 7b is a cross-sectional view of the bottom of the anodized aluminum hole and the titanium nitride interface. It is shown that there is an isolated circular island between anodized aluminum and titanium nitride. 1. electron energy loss spectrometer

Loss Spectrometer (EELS) analysis confirmed that the composition of this island A was oxidized oxide 'interface B was composed of titanium oxide and titanium nitride, and the group of the bottom layer c was titanium nitride. FIG. 8 is a SEM photograph showing the titanium oxide nano-dot array obtained after the anodized aluminum is removed at a later time. As shown in Fig. 8, the size y distribution and arrangement of the titanium oxide nano-points correspond to the anodized aluminum pores, showing that the oxygen-polar oxidation reaction of the titanium nitride layer occurs only in the nano-pores. The density of the titanium oxide quantum dots prepared by the present invention is extremely high, and the size of the quantum dots can be controlled by the anode oxidation parameters.

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Embodiment 2 The second embodiment of the present invention uses the regular arrangement of the titanium oxide nano-dot array 122 as a mask in the first embodiment, and etches the lower film 110 to form a nano-dot array with the same arrangement and different materials. . Figures 9 to 12 are cross-sectional views showing the process of a regularly arranged nano-dot array according to a second embodiment of the present invention. Referring to FIG. 9, a substrate 100 is provided, such as a Shixi substrate. A thin film 110, such as SiGe or a III-V compound semiconductor, is deposited on the substrate ιo. Next, a conductive layer 12 is deposited, such as Ti, TiN, co, Zn,

Cr, W, V, Cu, Mo, Fe or 111, preferably Ti or TiN, on the film 110. A preferred deposition method is a sputtering method or a reactive ion sputtering method, with a deposition temperature of 400 to 500 ° C and a thickness of 100 to 300 angstroms (A). Next, a metal layer 140, such as metal aluminum, is formed on the conductive layer 120. The preferred one is by thermal evaporation, deposition temperature of 200 ~ 30 (rc, thickness of 5 ~ 6 microns (

Next, the substrate 100 is placed in a vacuum annealing furnace and annealed at 500 π for 8 hours, so that the crystal structure of the metal layer 140 is dense and complete. Then, the surface polishing process of the metal aluminum layer 14 is performed by an electrolytic polishing step. The above-mentioned electrolytic polishing step is preferably performed by using a peroxyacid / ethanol solution as an electrolyte, a peroxyacid: ethanol system of 1: 4, a voltage of 40 volts (V), and performing the process at room temperature for 5 to 10 seconds. Please refer to FIG. 10 for the anodic oxidation treatment step of the metal aluminum layer 丨 40, and the metal aluminum layer 140 is oxidized to a% anodic aluminum oxide (ΑΑΟ) 140 with regularly arranged nanopores ^ 142, , Used as a template for the subsequent formation of titanium oxide nano-dot array. When the anode

1220539 V. Description of the invention (9) Subject to the scope of the attached patent application. Page 14 0522-10162TWF (Nl); jamngwo.ptd 1220539

Figures 1 to 4 are cross-sectional views showing the process of a regular array of titanium oxide nano-dot arrays according to the first embodiment of the present invention; Figure 5 is a diagram showing the relationship between the current density and time (j-t) during the anodization reaction; Figure 6a: Top view SEM photo of anodized aluminum nanopores; Figure 6b shows SEM photo of cross section of anodized aluminum nanopores; TEM photo; Figure 7a shows the bottom of the anodized aluminum hole and the titanium nitride interface Figures: • Figure 7b shows the cross section of the bottom of the anodized aluminum hole and the titanium nitride interface. Figure 8 shows the SEM photograph of the titanium oxide terameter dot array obtained after etching and removing the anodized aluminum; FIG. Is a cross-sectional view showing a process of a regular array according to a second embodiment of the present invention. Non-wood dots [Symbol description] 100 ~ substrate; 11 0 ~ SiGe film; 11 2 ~ nano dot array;

120 ~ conductive layer; 1 2 ~ 2 titanium oxide nano dot array; 1 40 ~ metal layer; 140 ~ anodized aluminum oxide (AA〇); 1 2 2 ~ anodized aluminum hole.

Claims (1)

1220539, the scope of the patent application: a method of making a regular array of nano-point arrays, including the following steps to provide a base to form a guide to form a gold for the anode-nano-level holes and continuously move the oxide mold hole array correspondingly Except the manufacturing method of Cr2, as applied, Cr, W, V, Cu 3. The manufacturing method of Cr, W, and 4. The manufacturing method of Cr, W, V, and Cu, and the polishing step. 5. The manufacturing method according to the application, alumina (ΑΑ0) < 6. The manufacturing method according to the application, bottom; the electrical layer is on the metal layer on the oxygen anodizing plate of the oxidation treatment array, and one of the metal meters is a hole The scope of patents includes the Mo and Fe patents, the scope of gold patents is on the anode substrate; on the conductive layer; step 'oxidizing the metal layer on the surface to form a compound template; processing steps, and passing through the nano-level hole array The surface of the conductive layer is oxidized to form a nano-point array of nano-scale pore oxides; and an oxide template of the array. The regular array of nano-dot arrays described in item 1 is composed of Ti, TiN, Co, Zn, Sn, or In. The regular array of nano-dot arrays described in item 1 is a layer material. The regular array nanometer dot array polar oxidation treatment step described in item 1 further includes an electrolytic patent range. The regular array nanometer dot array described in item 1 wherein the oxide template of the nanoscale hole array is the patent scope of the anode The regular array of nanometer dot arrays described in item 1, wherein the oxide template of the nanoscale hole array and the guide 0522-10162TWF (Nl); jamngwo.ptd page 16 6. Scope of patent application The interface between the electrical layers includes an oxide barrier. The method includes the following steps: a step of regularly arranging nano dot arrays, a method of fabricating, providing a substrate, forming a thin film on the substrate, forming a conductive layer on the thin film, and forming a metal layer on the conductive layer. Performing an anodic oxidation treatment step on an oxide template of a nanometer-sized hole array; oxidizing the metal layer to form an anodizing treatment step continuously; One of the metal oxide holes corresponding to the nanometer-sized hole array is vaporized to form a ^ = point array that is removed from the nanometer-sized hole array by the nanometer-sized holes; the converted part leaves the metal oxide template and The conductive layer is converted to a nanometer dot array by using the metal oxide nanometer; = column; by using a thin film. "Ma mask, etch the film to make the 8 · as in the patent application No. 7 production method, wherein the film is a regular array of nano dot arrays of $ · G 4 9. If the patent application is No. ', the production method Wherein, the nano-point arrays Cr, W, V, Cu, and M are regularly arranged as described in the guide. The nT layer system is Ti, TiN, and C. , Zn, Sn, 10. If the scope of the patent application is the second; 2 constitute. The manufacturing method, wherein the regular array of nano dot arrays described in the Jinli & item 11 · The regular array of nano dot arrays described in the patent application leaf line aluminum f item i 0522-10162TWF (Nl); jamngwo. ptd page 17 1220539 々, a method of making a patent application _, wherein the anodizing step is a polishing step. Xiangzhi also includes an electrolysis 1 2 · The method of making the item γ of Shenyan ’s patent, the nano-holes are regularly arranged in the nano-point array oxidation tank 0). The oxide template of J is the anode 13. The manufacturing method of item 7 of the patent application Fanyuan, wherein the interface between the nano-scale holes and the regular arrangement of the nano-dot array electrical layers includes _ gaseous ^ ^ gas of the column Template and the guide P hand layer0 0522-10162TWF (N1); j amngwo.p t d