[ Microscale Patterning with Photolithography and Wet Etching Processes ]

Chemical Engineering
■과 목 명: Laboratory 1

■담당교수: 박재형

■제 출 일: 2022/10/03
■학 과: 화학/고분자 공학과

■ 학 번 :
■성 명:
1. Title: Microscale Patterning with Photolithography and Wet Etching Processes
2. Objective
The object of eighth experiment is to understand the mechanism of producing micro-scale
patterns in semiconductor with photolithography which fabricating micro-scale patterns process
and wet etching process.
3. Theoretical Background
1) Photolithography
Photolithography has several processes. Details and the purpose of the process are as follows.
(1) Vapor prime with Surface cleaning / Treatment: Si wafer has a naturally formed oxide film
that must be removed during the cleaning process. Pollutants and air bubbles are also
removed during this process. In addition, the surface is treated with hydrophobicity during
the surface treatment process. The reason for treating it as hydrophobic is to make photo
resist adhere well. HMDS is used in this process. If this material is vaporized and coated on
the wafer, the wafer can be made hydrophobic.
(2) Photo resist coating: In this process, the photoresist is uniformly applied on the wafer. This
is very important point in this procedure. This is the process of making thin film using
centrifugal force of PR placed on the substrate. Using spin coating, the thickness,
absorbance, and refractive index of the thin film can be easily adjusted. As
the rotation speed increases, the thickness of the thin film decreases.
During procedure, Vacuum chuck would fix the wafer. However, since spin
coating uses centrifugal force, PR is thickly applied to the edge, and additional work is
needed.
(3) Soft baking: About 80% to 90% of solvent present in the photoresist is evaporated by
thermal energy to maintain a solid resist film state. If this process is not performed properly,
the solvent evaporates in the exposure step and contaminates the mask or stepper.
(4) Mask alignment and exposure: Mask alignment is the operation of aligning the mask and
the wafer after moving the wafer to the exposure facility. Only when this process is properly
performed the PR pattern can be engraved on the wafer in the
correct position, otherwise the characteristics of the device
deteriorate or the yield decreases. Next procedure is exposure by
stepper. In this process, UV or EUV is used to cause the
photochemical reaction of photoresists to be selective only in the
exposed area thanks to mask. It is to keep overlay accuracy with pre-
made patter.
(5) Post exposure bake (PEB): There is a photo active compound (PAC) in PR. After passing
the exposure step, PAC exists unevenly above and below the exposed part, and the
difference in concentration of PAC can be reduced by thermal energy through PEB.
(6) Develop: An alkali solution (TMAH) is used as developer to activate a
chemical reaction due to the difference in solubility between the
exposed and non-exposed regions. The development part varies
depending on positive PR and negative PR. In positive PR, chain
scission occurs in the light-hit area. Originally, positive PR is insoluble
in developer but after exposure, the polymer decomposes and
becomes soluble in the developer. So, the light-hit part dissolves
and disappears during the development process. By contrast
in negative PR, Cross-link occurs in the lighted area.
Originally, negative PR is soluble in developer but after exposure,
the polymer sticks together resulting in insolubility in developer.
 (7) Hard Baking: Heating the wafer to a high temperature (110oC~120oC) to volatilize the
residual developer and rinsing solution remaining after development process and remove it.
In this process, etching and adhesive ability of PR are also improved.
(8) Inspection: Check the process quality of the patterned results. The main points to be
checked are critical dimension, overlay accuracy, resist pattern profile, and the presence of
defect.
2) Etching
The etch process is an operation of removing an unnecessary oxide film by using an etchant of
liquid or gas. Here, if etchant is an acid base and caustic solution, it is called wet etch. Or if
etchant is a gas form, it is called dry etch. The reason why etching should be done well is because
it is directly related to yield. points to consider when performing the etching process are ① High
Etch rate, ② High Mask/Film Selectivity, ③Uniformity, ④Minimal Damage, ⑤Low contamination,
⑥Safety. When the uniformity is good, the degree of etching is the same for each part of the
circuit, so that the chips operate well in all parts. The following are the advantages and
disadvantages and characteristics of Dry etch and Wet etch.

Dry Etching Wet Etching

Method Physical & Chemical etching Chemical etching

Advantage 1) Anisotropic Etching which wouldn’t 1) Cheap

make under cut
2) Almost no lattice damage
2) Easy Automation
3) High selectivity
3) Safer Process
4) High etch rate
4) Excellent Reproducibility
5) Less complicated equipment

Disadvantage 1) Lattice damage 1) Isotropic Etching which would make

under cut
2) Low selectivity
2) Risk of contamination of wafers
3) Expensive
3) cannot be used in a process which
4) Low throughput requires feature size under 3
micrometers.
4) Require large amount of chemical
material
Characteristic

3) Undercut
The Undercut is a phenomenon in which an oxide film of an undesired part is
removed during wet etching. As mentioned earlier, one of wet etching’s
disadvantages is isotropic, which shaves off the unwanted parts as follows. This
gets worse when etchant is applied for too long. In this experiment, we use wet
etching, but companies also use Reactive Ion Etching (RIE) to make up for the shortcomings of
dry etching and wet etching.

4. Apparatus & Reagent

1) Apparatus
1. Spin coater: Apparatus to make uniform and even thin film on substrate (wafer). Put the PR on
the middle of wafer and control rotation speed which decide thickness of thin film.
2. UV exposure: Apparatus that make a radiation to make a pattern on photoresist after using spin
coater. Depending on type of PR, removing part varies.
3. Cr MASK: Apparatus to make patterns on photoresist during exposure procedure. It is pre-
made mask and radiation from UV exposure cannot pass through Cr MASK.
4. Microscope: Apparatus to check that the pattern is well formed after this experiment. The
sample we made is too small to check the pattern with our eyes.
5. Chemical Hume Hood: Apparatus to protect our body from dangerous reagents. Because we
use Buffered Oxide Etch and Developer-AZ400K that are harmful to our body, we must use
Chemical Hume Hood.

2) reagents
1. Wafer(C-Si) (Crystalline silicon)
Wafer refers to a disk that a single crystal pillar made by growing Si, GaAs, then be thinly cut to an
appropriate thickness. This becomes the basic material for the semiconductor integrated circuit. It
is not a dangerous substance when checking MSDS, but it may be irritating when it touches the
skin. And since it is a thin plate, we should pay attention so that we don’t break it.
 2. Buffered Oxide Etch (NH4F+HF)
During etching procedure, we use this as wet etchant. It is used to etch thin films composed of
Si3N4 and SiO2. I regard MSDS of BOE as sum of NH4F and HF. It is harmful material when inhaled
and touched. So, wear a glass and glove before use it. Melting point: 18°C / Boiling point: - /
Molecular weight: Not applicable to mixture / Density(20°C): Not applicable to mixture / Solubility in
water(20-30°C): soluble
H301, H331- Toxic if swallowed or inhaled, H319- severe irritation to the eyes, H250- Self-ignition
when exposed to air

3. PR-AZ1512(C6H12O3) (1-Methoxy-2-propyl acetate)

PR-AZ1512 is positive PR. So, chain scission occurs in the light-hit area. The polymer in PR-
AZ1512 decomposes and becomes soluble in the developer after exposure. It is flammable and
cause respiratory irritation. Wear a mask and be careful. Melting point: -87°C / Boiling point: 146°C
/ Molecular weight: 132.16g/mol Density(20°C): 1.04g/cm3 / Solubility in water(20-30°C): 19.8g/L
H226 - Flammable liquids and vapors, H335 - May cause respiratory irritation, H336 - May cause
drowsiness or dizziness

4. DEVELOPER-AZ400K (B4K2O7 + KOH + H2O)

I regard MSDS of DEVELOPER-AZ400K as sum of B 4K2O7 and H2O. After performing the
Exposure and PEB processes, if this material is used, the PR of the light-hit part can be removed
because we use positive PR. It is harmful material when inhaled and touched
H226- Flammable liquid and vapor. H319-Causes serious eye irritation. Next information is about
safranin. Melting point: 0°C / Boiling point: 100°C / Molecular weight: Not applicable to mixture /
Density(20°C): Not applicable to mixture / Solubility in water(20-30°C): soluble
5. D.I. Water (H2O)
It is used to soak the Wafer. It is not harmful.
Melting point: 0°C / Boiling point: 100°C / Molecular weight: 18.02g/mol
Density(25°C): 0.997g/cm3 / Solubility in water(20-30°C): -

5. Experimental Procedure
1. Cleaning Process. ➀ Dip the wafer in the DI water (minimum 10min) ➁ The wafer is cleaned by
acetone, IPA, DI water sequentially and by N2 gas to dry the surface. - Since the patterning
process takes place in very small units of size, the cleaning process is very important. Even small
dust can be highly involved in the experimental results. It should be cleaned through Acetone and
IPA and dried well to prevent air bubbles through the N2 gas air blower.
2. Lithography Process ➀ PR doping process: Step 3 of the PR-AZ1512 Run Spin coating STEP
1: RPM 2000, 5sec STEP 2: RPM 1000, 40sec STEP 3: RPM 2000, 5sec - Adjust the rotation
speed and adjust the thickness and uniformity of PR. Foil prevents photoresists from splashing on
spin coater. Tape strengthens the adhesion between the wafer and the spinning spin coater so that
it does not fall off. ➁ Soft baking process: Put the wafer on heating plate (120oC, 90sec) - About
80% to 90% of solvent present in the photoresist is evaporated by thermal energy. It’s hot so be
careful. ➂ Photo process: Channel and a mask in the name of your release is after the exposure
to UV Exposure (Vacuum, 300sec) ➃ Develop process: Soak in Developer-AZ400K ➄ Hard
baking process: Put the wafer on heating plate (120oC, 90sec) – Because we use PR-AZ1512
which is positive PR, exposed part will be soluble in developer.
3. Wet etching process ➀ Dip the wafer in the BOE solution. ② As soon as you remove the wafer
from the BOE solution, soak it in DI water. ③ Remove the wafer from DI water and remove DI
water using N2 gas. – Be careful not to be over etched by applying BOE too long time.
4. Pattern observation with a microscope ① Cut the wafer for observation. ② Put it on the stage. ③
Observe the cross section.

6. Pre-Lab Report
1. Discuss the working principle of photolithography and wet etching.
By Photolithography, we can make pattern on the wafer using UV, etchant, developer, and PR.
Process of photolithography is written in detail in Theoretical Background.
We can remove SiO2(Oxide film) on a wafer using BOE solution in this experiment during Wet
etching. Remained PR can act as a shield. Only the part of oxide film disappears without PR that
removed in development procedure. This is a common part of etching. In the case of wet etching,
it goes through three steps. ① Liquid etchant is diffused. ② Redox reaction occurs between the
diffused liquid etchant and the oxide film. In this process, the oxide film melts and disappears. ③
The by-product produced in the reacted place diffuses.
2. Discuss the critical factors (temperature, time, RPM, UV wavelength, etc.) of photolithography
process and wet etching process.

3) Submit cross section picture of etched wafer

 The result will be the same as the next picture.
This is the result picture of the procedure part of
the i-campus.

7. References
1. ScienceDirect; Spin-coating - Advantages of spin coating
2. [Link] - Simple instruction of two types of bacteria’s structure
3. Sungkyunkwan University of Chemical Engineering, Chemical Engineering Laboratory 1,
p.40~44
4. [Link] - MSDS information of Reagents.
5.[Link]
effect_fig1_26842249 - Figure of Edge Bead
6.[Link]
vlsi.769721/ - Figure of difference of positive / negative PR