Sapphire details
     The composition of sapphire is alumina (Al2O3) , which is a combination of three oxygen atoms and two aluminum atoms in a covalent bond . Its crystal structure is a hexagonal lattice structure . It is often used in A-Plane. C-Plane and R-Plane. Because sapphire optical transit wide band from near-ultraviolet light (190nm) to the infrared rays have good translucency. Thus the optical element is used in a large amount, infrared devices, high strength Laser lens material and reticle material, it has high sound speed, high temperature resistance, corrosion resistance, high hardness, high light transmission, high melting point ( 2045 °C), etc. It is a very difficult material to be processed, so it is often Used as a material for photovoltaic elements. The quality of ultra-high brightness white / blue LEDs currently depends on the material quality of gallium nitride epitaxial (GaN) , while the gallium nitride epitaxial quality is closely related to the surface quality of the sapphire substrate used, sapphire ( single crystal Al2O3)C The lattice constant mismatch between the surface and the III - V and II - VI deposited films is small, while conforming to GaN   The high temperature resistance requirements of the epitaxial process make the sapphire wafer a key material for making white / blue / green LEDs .

The following figure is a cutaway view of sapphire; a top view of the crystal structure; a side view of the crystal structure; a structural diagram of Al2O3; a schematic view of the crystal surface of sapphire
Sapphire map
Sapphire Figure 1

Sapphire crystal surface diagram

The most commonly used GaN epitaxial is the non-polar surface of C-plane (0001), so the polarity of GaN will be determined by the process.

GaN epitaxial

Sapphire (Al2O3) Characteristics Table

Molecular formula

Al2O3

density

3.95-4.1 g / cm 3

Crystal structure

Hexagonal lattice

Lattice constant

a=4.785Ã…, c=12.991Ã…

Moh's hardness

9 (after diamond only: 10)

Melting point

2045°C

Boiling point

3000 ° C

Thermal expansion coefficient

5.8×10 -6 /K

Specific heat

0.418Ws/g/k

Thermal conductivity

25.12W/m/k (@ 100°C)

Refractive index

No =1.768 ne =1.760

Dn/dt

13x10 -6 /K (@633nm)

Light transmission characteristics

T≈80% (0.3~5μm)

Dielectric constant

11.5(∥c), 9.3(⊥c)


2 sapphire crystal growth method

There are two common methods for growing sapphire crystals:

1: Czochralski method (Czochralski method), referred to as CZ method. The raw material is heated to the melting point and then melted to form a molten soup, and then a single crystal seed crystal is used to contact the surface of the molten soup, and the solid solution of the seed crystal and the molten soup. The interface is too cold due to the temperature difference. The melt then begins to solidify on the surface of the seed crystal and grow and crystallize the single crystal of the same crystal structure. The seed crystal is pulled up at a very slow speed and rotates with a certain rotation speed. As the seed crystal rises upward, the melt gradually solidifies on the liquid-solid interface of the seed crystal, thereby forming an axisymmetric single. Crystal ingots.

2: Kyropoulos method (Kyropoulos method), referred to as KY method, the continent is called the bubble method. The principle is similar to Czochralskimethod. The raw material is heated to the melting point and then melted to form a melt. Single crystal seed crystals (SeedCrystal, also known as seed crystal rods) contact the surface of the molten soup, and begin to grow and crystallize the single crystal of the same crystal structure at the solid-liquid interface between the seed crystal and the molten soup. The seed crystal is extremely slow. The speed is pulled up, but the seed crystal is pulled up for a period of time to form a crystal neck. After the solidification rate of the melted soup and the seed crystal interface is stabilized, the seed crystal is no longer pulled up, and there is no rotation, only to control Cooling rate mode to make the single crystal gradually solidify from above, and finally solidified into a whole single crystal germanium.

The crystal growth diagrams of the two methods are as follows:
Crystal growth diagram
Schematic diagram of the Czochralski method
Kelvin crystal growth method
3 sapphire substrate processing

The raw material of the sapphire substrate is an ingot, and the ingot is processed from sapphire crystal. The related manufacturing process is as follows:

Sapphire crystal rod manufacturing process
Sapphire crystal rod manufacturing process sapphire crystal rod processing Sapphire crystal rod processing

Growth: Crystal growth of large-size, high-quality single crystal sapphire crystals using a crystal growth furnace

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Orientation: Ensure the correct position of the sapphire crystal on the crowbar table for easy pry bar processing

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Crowbar: Sapphire crystal rods are extracted from sapphire crystals in a specific way

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Barrel grinding: Cylindrical grinding of the ingot with a cylindrical grinder for accurate outer circle dimensional accuracy

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Quality inspection: Ensure the quality of the ingot and the size and orientation of the ingot after the picking are in accordance with customer specifications.

Crystal rod

Orientation: Accurately position the sapphire ingot on the microtome for precise slicing

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Slicing: cutting a sapphire ingot into a thin wafer

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Grinding: cutting the damaged layer caused by the wafer and improving the flatness of the wafer

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Chamfer: Trim the edge of the wafer into an arc shape to improve the mechanical strength of the edge of the sheet and avoid defects caused by stress concentration

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Polishing: Improve the roughness of the wafer to achieve the accuracy of the epitaxial wafer epitaxial level

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Cleaning: Remove contaminants from the surface of the wafer (eg, dust particles, metals, organic contaminants, etc.)

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Quality inspection: Inspection of wafer quality (flatness, surface dust particles, etc.) with high-precision testing instruments to meet customer requirements

4 sapphire substrate application types

The sapphire substrates used by the majority of epitaxial wafer manufacturers are divided into three types:

1:C-Plane sapphire substrate

This is the sapphire substrate surface commonly used by GaN for the growth of GaN. This is mainly because the sapphire crystal grows along the C-axis, the process is mature, the cost is relatively low, the physicochemical properties are stable, and the technology for epitaxial growth on the C-plane is mature and stable.

2: R-Plane or M-Plane sapphire substrate

It is mainly used to grow non-polar/semi-polar GaN epitaxial films to improve luminous efficiency. The GaN epitaxial film usually prepared on a sapphire substrate is grown along the c-axis, and the c-axis is the polar axis of GaN, resulting in GaN. A strong built-in electric field appears in the active layer quantum well of the base device, and the luminous efficiency is thus reduced. The non-polar surface GaN epitaxy is developed to overcome this physical phenomenon and improve the luminous efficiency.

3: Patterned Sapphire Substrate (PSS)

In the form of growth or etching, a nano-specific regular microstructure pattern is designed on the sapphire substrate to control the output light form of the LED, and at the same time reduce the difference between the GaN grown on the sapphire substrate. Discharge defects, improve epitaxial quality, and improve the internal quantum efficiency of LEDs and increase light extraction efficiency.

1:C-Plane sapphire substrate

The C-Plane sapphire substrate is a commonly used sapphire substrate. In 1993, Professor Akasaka Yoshi of Japan and Dr. Nakamura Shuji of Nichia Chemical at that time broke through the lattice mismatch (buffer layer) and p-type material of InGaN and sapphire substrate. After activation and other issues, Nichia was finally able to develop blue LEDs at the end of 1993. In the following years, Nichia Chemical used sapphire as a substrate, using InGaN materials, and continuously improved sapphire substrate and epitaxial technology through MOCVD technology. To improve the luminous efficiency of blue light, and at the same time, UV LEDs were developed in 1997. In 1999, blue-violet LED samples began to be shipped. In 2001, white LEDs were introduced. This laid the foundation for Nichia's leading position in the LED field.

Taiwan closely follows Japan's LED technology. Taiwan's LED development first purchased epitaxial wafer processing from Japan, and then bought MOCVD machines and sapphire substrates for epitaxy. Later, local Taiwanese manufacturers studied the growth and processing technology of sapphire crystals. Production, through independent research and development, to obtain LED patent authorization and other means to achieve sapphire crystal, substrate, epitaxial wafer production, epitaxial wafer processing and other independent production technology capabilities, step by step to establish Taiwan's important position in the LED upstream business.

At present, most of the blue/green/white LED products are products that are produced by MOCVD epitaxy using sapphire substrates represented by Japan and Taiwan. The sapphire substrate is very common, and the US CREE company uses SiC as the substrate. The representative LED products follow.

2: patterned sapphire substrate
(Pattern Sapphire Substrate referred to as PSS)

Designing micro- or nano-scale micro-structure-specific patterns on sapphire substrates by etching (in sapphire C-face dry etching/wet etching) to control the output light form of LEDs (on sapphire substrates) The concave-convex pattern produces a light scattering or refraction effect to increase the light extraction rate), and the GaN film grows on the patterned sapphire substrate to produce a lateral epitaxial effect, which reduces the difference in defects between GaN grown on the sapphire substrate, and improves The epitaxial quality improves the internal quantum efficiency of the LED and increases the light extraction efficiency. Brightness is increased by more than 70% compared to LEDs grown on general sapphire substrates. At present, Taiwan produces patterned sapphire with Sino-US twin, crystal, and mega crystal. 2/4 inch of the sapphire substrate is a mature product, the price is gradually stable, and the large size (such as 6/8 inch) ordinary sapphire substrate With the 2-inch patterned sapphire substrate in the growth period, the price is also high, and its manufacturer is also the main push large size and patterned sapphire substrate, while also actively increasing production capacity. At present, no manufacturer in the mainland can produce patterned sapphire substrates.

Figure 9: Nanopatterned sapphire substrate
Nano patterned sapphire substrate
3: R-Plane or M-Plane sapphire substrate

Generally, a GaN thin film grown on a C-plane sapphire substrate grows along its polar axis, ie, the c-axis direction, and the film has spontaneous polarization and piezoelectric polarization effects, resulting in a strong inside of the thin film (active layer quantum well). The built-in electric field (Quantum Confine Stark Effect, QCSE; history tank effect) greatly reduces the luminous efficiency of GaN films. GaN thin films grown on some non-C-plane sapphire substrates (such as R-plane or M-plane) and other special substrates (such as lithium aluminate; LiAlO2) are non-polar and semi-polar, as caused by the polarization field. The negative effects produced in the illuminating device will be partially or even completely improved. Traditional three-five nitride semiconductors are grown on c-plane sapphire substrates. If these compounds are grown on R-plane or M-Plane, the built-in electric field can be generated parallel to the epitaxial layer to increase the electron power. The probability of a hole in the compound. Therefore, the growth of the LED structure based on the nitride epitaxial film on the R-plane or M-Plane sapphire substrate can effectively solve the problem of low efficiency of the quantum efficiency of the LED compared to the conventional C-plane sapphire epitaxy. Increase the luminous intensity of the component. The latest news is said that non-polar LEDs can double the luminous efficiency of white light.

Since non-polar GaN has more potential than traditional c-axis GaN to produce high-efficiency components, many international manufacturers and research units have increased the research and production of such epitaxial technology. Therefore, the demand and requirements for R-plane or M-Plane sapphire substrates are correspondingly increased.

Figure 10: Simple schematic of a semi-polar and non-polar surface

The non-polar surface refers to the surface in the normal direction of the polar surface, and the semi-polar surface is the surface between the polar surface and the non-polar surface.
Simple schematic of semi-polar and non-polar faces
5 main technical parameters of sapphire substrate

Due to different technologies and processes, epitaxial wafer manufacturers have different requirements for sapphire substrates, such as thickness and crystal orientation.

Below are some basic technical parameters for sapphire substrates produced by several manufacturers (using a mature C-plane 2 inch sapphire substrate as an example). More is that the epitaxial wafer manufacturers customize the sapphire substrate to meet the requirements of their own use according to their own technical characteristics and the quality requirements of the epitaxial wafers produced. That is, customer customization.

They are: A: Taiwan Taoyuan Zhaojing Technology Co., Ltd.

B: Taiwan Hsinchu Zhongmei Jingjing Products Co., Ltd.

C: American Crystal Systems

D: Russia Cradley Crystals

A: Technical parameters of C-side 2 inch sapphire substrate of Taiwan Zhaojing Technology Co., Ltd.
2-inch sapphire substrate

Item Item

Specifications

Material

High purity (> 99.996%)

Single crystal Al2O3,

Crystal orientation Orientation

C axis (0001) ± 0.3 °

Diameter Dismeter

50.8±0.2mm

thickness Thickness

330μm/430μm±25μm

Total thickness deviation TTV

<10μm

Warpage BOW

<10μm

Positioning plane direction

Primary Flat Location

Side A (11-20) ± 0.5 °

Positioning side length

Primary Flat Length

16±1.2mm

positive

Front Surface

Epi-ready polished

(Extension open box ready to use)

Surface roughness

Surface Roughness

Ra<0.3nm

back Backside

Ra=0.5~1.2μm

package Package

Clean indoor vacuum nitriding package

B: Technical parameters of C-side 2 inch sapphire substrate of Taiwan Zhongmei Jingjing Products Co., Ltd.

Item Item

Specifications

Material

High purity single crystal Al2O3,

Crystal orientation Orientation

C plane (0001) ± 0.3 °

Offset angle to the M axis

Off-set Angle toward M-axis

0.20 ± 0.05°

Offset angle to axis A

Off-set Angle toward A-axis

0.0 ± 0.1°

diameter Dismeter

50.8±0.15mm

thickness Thickness

430μm±15μm

Total thickness deviation TTV

<10μm

Surface total flatness TIR

≦ 10μm

Curvature WARP

≦ 15μm

Warpage BOW

-10 ~ 0μm

Positioning plane direction Primary Flat Location

Side A (11-20)

Positioning surface deviation angle Flat Off-set Angle

0.0 ± 0.2°

Positioning side length Primary Flat Length

16±0.5mm

Surface roughness Frontside Surface Roughness

RA≦ 3Å (ie Ra≦0.3nm)

Back roughness Backside Surface Roughness (Ra)

Ra=0.5~1.0μm

package Package

Clean indoor vacuum nitriding package

C: Technical parameters of C-side 2 inch sapphire substrate of Crystal Systems, USA

Item Item

Specifications

material Material

High purity single crystal Al2O3 >99.99%

Crystal orientation Orientation

C axis (0001) ± 0.2°

diameter Dismeter

50.8±0.15mm

thickness Thickness

330μm/430μm±25μm

Total thickness deviation TTV

≦ 25μm

Warpage BOW

≦ 20μm

Positioning edge direction Primary Flat Location

A axis (11-20) ± 0.3°

Positioning side length Primary Flat Length

16±1.5mm

positive Front Surface

Fine polishing (out of the box)

Finishing polishing epi-ready

Surface Roughness (Ra)

Ra<1nm

back Backside

Fine grinding Fine grind Rmax 5-10 μm

package Package

Class 100 clean room nitrogen packaging 5/10/25 piece boxed

D: Russia Cradley Crystals C-side 2 inch sapphire substrate technical parameters

Item Item

Specifications

material Material

High purity single crystal Al2O3 >99.99%

Crystal orientation Orientation

C axis (0001) ± 0.2°

diameter Dismeter

50.8±0.1mm

thickness Thickness

330μm/430μm±25μm

Total thickness deviation TTV

≦ 10μm

Warpage BOW

≦ 5μm

Positioning edge direction Primary Flat Location

A axis (11-20) ± 0.3°

Positioning side length Primary Flat Length

16±0.8mm

positive Front Surface

Fine polishing (out of the box)

Finishing polishing epi-ready

Surface Roughness (Ra)

Ra<0.3nm

back Backside

Fine grinding Fine grind Ra<1μm or 80/50polishing

package Package

Class 100 clean room nitrogen packaging 25 pieces boxed

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