A REPORT ON ATOMIC LAYER DEPOSTION AND MOLECULAR BEAM EPITAXY Submitted in partial fulfillment for award of the degree

of MASTER OF TECHNOLOGY IN NANOTECHNOLOGY( ELECTROMECHANICAL)

Session 2013-2014

SUBMITTED TO:
Faculty Name : Mr. Shobhi Bhagga sir Designation : Department : Assistant Professor Dept. of Nanotechnology

Submitted By:
Students Name : Nemi chand Sood College ID : 12/986

DEPARTMENT OF NANOTECHNOLOGY CENTRE OF NANOTECHNOLOGY, RTU KOTA (RAJASTHAN)

ACKNOWLEDGEMENT
I would like to acknowledge and extend my heartfelt gratitude to the following persons who have made the completion of this Lecture Notes possible. Our HOD, DR. ANIL PATHAK SIR ,for his vital encouragement and support. Mr. SHOBBI BHAGGA SIR and Ms. SANJU TANWAR MADAM Assistant Professor, for their understanding and our

assistance.

All CENTER OF NANOTECHNOLOGY,RTU,KOTA faculty members and Staff. For their constant reminders and much needed motivation or for the help and inspiration he extended. I am obliged to staff members of RRCAT, for the valuable information provided by them in their respective fields. I am grateful for their cooperation during the period of my tour. And to God , who made all things possible.

ABSTRACT
We have visited Raja Ramanna Centre for Advanced Technology(RRCAT),Indore for knowing about the advanced technology which are used in various field such as nanotechnology. In our schedule first day we headed to the Conference room and were briefed about the Centre by a presentation on synchrotron radiation facilities and synchrotron radiation sources Indus-1 and Indus-2 being built at RRCAT. The honors were done none other than Dr. S. K. Deb Head, Indus Synchrotrons Utilization Division. We were also briefed about the variety of laser systems facilities available at RRCAT and its various possible applications then start visit the characterization lab (SEM,TEM,FIB,Etching).Then know about synchrotron radiation in INDUS 1 and INDUS 2 which used only in indore throughout the india for different techniques. Second day of our visit we have visited the UHV Section in which we know about different pumps(rotary,turbomolecular,sputter ion and titanium sublimation pump ) and gauges. Then we go to the Laser section in which different kinds of synthesis process of nanomaterials using laser and chemical route(sol gel,PLD,ALD).

CONTENTS

1. INTRODUCTION 2. FUNDAMENTAL OF MOLECULAR BEAM EPITAXY 3. TYPES OF MOLECULAR BEAM EPITAXY 4. ADVANTAGE AND DISADVANTAGE 5. BASIC OF ATOMIC LAYER DEPOSTION

6. APPLICATIONS OF ATOMIC LAYER DEPOSTION 7. CONCLUSION.

INTRODUCTION
Raja Ramanna Centre for Advanced Technology was established by the Department of Atomic Energy, India to expand the activities carried out at Bhabha Atomic Research Centre (BARC), Mumbai, in two frontline areas of science and technology namely Lasers and Accelerators. On February 19, 1984 the President of India, Gyani Zail Singh, laid the foundation stone of the centre. Construction of laboratories and houses began in May 1984. In June 1986, the first batch of scientists from BARC, Mumbai, moved to RRCAT and scientific activities were started. Since then, the centre has rapidly grown into a premier institute for research and development in lasers, accelerators and their applications. The RRCAT campus is spread over a 760 hectare picturesque site on the outskirts of Indore city. The campus encompasses laboratories, staff housing colony and other basic amenities like school, sports facilities, shopping complex, gardens etc. RRCAT is involved in development of a variety of laser systems and their utilization for applications in industry, medicine and research. The laser systems developed include high power CO2 lasers, flash lamp and diode laser pumped Nd lasers, semiconductor lasers, chemical lasers, excimer lasers and high energy/intensity pulsed lasers. Crystals of a variety of materials of interest to laser technology have been grown. The industrial applications being pursued include cutting, drilling, welding, surface modifications and rapid manufacturing. Various laser based instruments such as uranium analyzer, land leveler, compact N2 laser, photo-coagulator, fibre based temperature sensor, surgical CO2 laser system have

been developed. Home-made and commercial lasers are being used for research in the areas of laser plasma interaction, laser-based charged particle acceleration, laser cooling and trapping of atoms, nonlinear optics, ultra-fast dynamics, material processing, laser fluorescence spectroscopy of tissues, effects of narrow bandwidth light on cells and animal models, imaging through turbid media, laser micromanipulation of microscopic objects etc.

Molecular beam epitaxy :MBE is a technique for the epitaxial growth of materials by means of the chemical interaction of one of the several molecular or atomic beams of different intensities and compositions that occurs on the surface of a heated single crystalline substrate. It is an ultra-high vacuum(UHV) based technique for producing high quality epitaxial structures with monolayer(ML) control. A schematic representation of a MBE apparatus is shown in figure. The source materials are placed in the evaporation cell which are composed of crucibles, resistive heaters and thermal screans. The shape and dimensions of the crucibles are such that they fulfil the requirement of angular distribution of atoms and molecules in a beam. The angular distribution of the beam and the distances between the sources and the substrate determine the homogeneity of the parameters of epilayers and hetrostructures grown by this technique. The whole MBE chamber is pumped down to ultra-high vacuum and the operation is also oil-free. Ultra high vacuum condition used to ensure the molecular beam condition, where the free path of the particle is larger than the geometrical size of the chamber. MBE system is also equipped with a reflection high-energy electron diffraction(RHEED) system and mass spectrometers for monitoring the beams, their molecular compositions and the residual atmosphere. MBE has evolved into one of the most widely used techniques for producing epitaxial layers of metals, insulators and superconductors as well, both at the research and the industrial production level. The principle undelaying MBE growth is relatively simple; it consists essentially of atoms or clusters of the atoms, which are produced by heating up a solid source.

Schematic drawing of a generic MBE system.

Surface Preparation :A clean surface is an important prerequisite for epitaxial

growth, since contaminants from the atmosphere or other sources can easily contaminate a clean GaAs wafer and cause crystal defects or degrade the optical and electrical characteristics of the epitaxial layer. Auger electron spectroscopy was an essential tool for determining wafer cleanliness as MBE was being developed [2], but most GaAs wafer vendors currently supply 'epi-ready' wafers which are pre-cleaned and oxidized in a controlled environment. The oxide forms a protective layer which can be removed inside the growth chamber. The use of such epi-ready wafers has lead to consistent results without the need for elaborate wafer cleaning procedures. To use samples of arbitrary size, wafers pieces are cleaved and then bonded using indium to molybdenum blocks. This handling will result in some dust on the wafer surface that will produce defects, but with proper care, the amount of dust can be reduced. The mounted samples are then put into the load lock and heated for several hours to outgas the samples and blocks before moving them into the buffer chamber. The samples are and outgassed again in the buffer chamber at 450C before they are moved into the growth chamber. Growth Rate Calibration :Beam Equivalent Pressure Calibration of the growth rate is essential for the proper tuning of resonant-cavity devices. There are several insitu techniques which can be used in MBE. One way to measure the growth rate is to use the BEP gauge. This measurement is dependent on factors such as the geometry of the system and ionization efficiency of the material being measured, but for a given system and material, the BEP reading is proportional to the flux at the sample surface and hence the growth rate. Unlike other techniques we can use, a BEP measurement does not require that any epitaxial layers be grown. Growing epitaxial layers requires an approximate knowledge of the flux beforehand, so the BEP is particularly useful for effusion cells which are being used for the first time. For the Varian Gen II, a BEP reading in the mid to high 10-7 Torr range gives Ga growth rates of about 1 m m/hour. There are limitations to this technique however. It is not a direct measure of the growth rate, so some other in-situ or ex-situ technique must still be used to relate the BEP to a growth rate. The resolution of the BEP gauge in our

Varian Gen II can only measure the rates to a precision of several percent. The biggest difficulty, however, is that while measuring the flux of a group III component, the gauge gets coated, causing a rapid loss of sensitivity in the gauge. The gauge sensitivity will eventually recover if left running under an As overpressure, but the measurement is thus uncertain and potentially timeconsuming if repeatability is desired.

ALD (Atomic Layer Deposition):ALD is a self-limiting (the amount of film material deposited in each reaction cycle is constant), sequential surface chemistry that deposits conformal thin-films of materials onto substrates of varying compositions. Due to the characteristics of self-limiting and surface reactions, ALD film growth makes atomic scale deposition control possible. ALD is similar in chemistry to chemical vapor deposition (CVD), except that the ALD reaction breaks the CVD reaction into two half-reactions, keeping the precursor materials separate during the reaction. By keeping the precursors separate throughout the coating process, atomic layer control of film growth can be obtained as fine as ~0.1 (10 pm) per cycle. Separation of the precursors is accomplished by pulsing a purge gas (typically nitrogen or argon) after each precursor pulse to remove excess precursor from the process chamber and prevent 'parasitic' CVD deposition on the substrate. Atomic Layer Deposition Atomic layer deposition, ALD, is a thin film technology that enables new and highly competitive products. ALD is also a powerful resource for advanced nanotechnology research. Typical applications of ALD contain a requirement to manufacture very precise nanometerthick, pinholefree and totally conformal thin films on any shape and geometry. For todays businesses, Beneq ALD offers the necessary tools to accelerate growth, by means of new and innovative applications, production equipment you can count on and affordable cost of ownership. ALD, a chemical vapor deposition (C VD) method, was initially developed for manufacturing nanolaminate insulators (Al2 O3 /TiO2 ) and zinc sulfide (ZnS) phosphor films for thin film electroluminescent (TFEL) displays. Largescale production of these displays started in the mid1980s, mainly thanks to ALD. The unique properties of the coatings, together with the high repeatability, were the main factors leading to successful industrial production.

Technology basics
ALD is an enabling technology for new and improved products. It provides coatings and material features which either cannot be achieved costefficiently with existing techniques, or they cannot be achieved at all. ALD, as a thin film coating method, offers: Precise control of the film thickness, at true nanometer scale Pinholefree films for, e.g., superior barriers and surface passivation C onformal coating of batches, large area substrates and complex 3D objects, including porous bulk materials, as well as powders Engineered and new functional materials and structures, such as nanolaminates A highly repeatable and scalable process.

ALD(Atomic Layer Depostion) Process :The growth of material layers by ALD consists of repeating the following characteristic four steps: 1. Exposure of the first precursor, typically an organometallic compound. 2. Purge or evacuation of the reaction chamber to remove the non-reacted precursors and the gaseous reaction by-products. 3. Exposure of the second precursor or another treatment to activate the surface again for the reaction of the first precursor, such as a plasma. 4. Purge or evacuation of the reaction chamber. Each reaction cycle adds a given amount of material to the surface, referred to as the growth per cycle. To grow a material layer, reaction cycles are repeated as many as required for the desired film thickness. One cycle may take time from 0.5 s to a few seconds and deposit between 0.1 and 3 of film thickness. Due to the self-terminating reactions, ALD is a surface-controlled process, where process parameters other than the precursors, substrate, and temperature have little or no influence. And, because of the surface control, ALD-grown films are extremely conformal and uniform in thickness. These thin films can also be used in correlation with other common fabrication methods. Typical process conditions: Pressure range: 0.110 mbar (Torr, hPa) or atmospheric Temperature: typically, 50 - 500 C

ALD cycle for Al2O3 deposited using TMA and O2 plasma.

Only step 3 varies between H2O for the thermal process or O2 plasma:
A. TMA chemisorbtion B. TMA purge C. O2 plasma D. Short post plasma purge

ALD Cycle Time

Cycle time

tcycle = tpulse A + tpurge A+ tpulse B + tpurge B

Purge time = time to remove unreacted or excess chemicals C(t) = C0exp(-tpurge/) Residence time, = V/S

ALD Precursor Requirements : Must be volatile and thermally stable Preferably liquids and gases Should Chemisorb onto the surface or rapidly react with surface and react
aggressively with each other

-Short saturation time, good deposition rate, no gas phase reactions Should not self-decompose - Affect thickness, uniformity Should not etch, dissolute into film or substrate.

Advantages and limitations :Advantages Using ALD, film thickness depends only on the number of reaction cycles, which makes the thickness control accurate and simple. Unlike CVD, there is less need of reactant flux homogeneity, which gives large area (large batch and easy scale-up) capability, excellent conformality and reproducibility, and simplifies the use of solid precursors. Also, the growth of different multilayer structures is straight forward. These advantages make the ALD method attractive for microelectronics for manufacturing of future generation integrated circuits. Other advantages of ALD are the wide range of film materials available, high density and low impurity level. Also, lower deposition temperature can be used in order not to affect sensitive substrates. Limitations The major limitation of ALD is its slowness; usually only a fraction of a monolayer is deposited in one cycle. Fortunately, the films needed for future-generation integrated circuits are very thin and thus the slowness of ALD is not such an important issue. More recently, commercial ALD tools can achieve cycle times of <5 seconds meaning a 100 nm film can be deposited in under an hour. With batch processing this can equate to a high throughput of wafers/minute. New advances in roll-to-roll ALD are allowing even faster throughput. Although the selection of film materials grown by ALD is wide, many technologically important materials (Si, Ge, Si3N4, several multi-component oxides, certain metals) cannot currently be deposited by ALD in a costeffective way.

 ALD is a chemical technique and thus there is always a risk of residues being left from the precursors. The impurity content of the films depends on the completeness of the reactions. In typical oxide processes where metal halides of alkyl compounds are used together with water as precursors, impurities found in the films are at the 0.1-1 atom % level.

Application :ALD can be used for many applications including:

High-k gate oxides Storage capacitor dielectrics Pinhole-free passivation layers for OLEDs and polymers Passivation of crystal silicon solar cells High aspect ratio diffusion barriers for Cu interconnects Adhesion layers Organic semiconductors Highly conformal coatings for microfluidic and MEMS applications Other nanotechnology and nano-electronic applications Coating of nanoporous structures Fuel cells, e.g. single metal coating for catalyst layers Bio MEMS