Table Of ContentMolecular Layer
Deposition for Tailored
Organic Thin-Film
Materials
This book provides concepts and experimental demonstrations for various types
of molecular layer deposition (MLD) and organic multiple quantum dots (organic
MQDs), which are typical tailored organic thin-film materials produced by MLD.
Possible applications of MLD to optical interconnects, energy conversion systems,
molecular targeted drug delivery, and cancer therapy are also proposed. First, the
author reviews various types of MLD processes including vapor-phase MLD, liquid-
phase MLD, and selective MLD. Next, he introduces organic MQDs. The author
then describes the design of light modulators/optical switches, predicts their perfor-
mance, and discusses impacts of the organic MQDs on them. He then also discusses
impacts of the organic MQDs on optical interconnects within computers and on opti-
cal switching systems. Finally, the author presents MLD applications to molecular
targeted drug delivery, photodynamic therapy, and laser surgery for cancer therapy.
This book is intended for researchers, engineers, and graduate students in opto-
electronics, photonics, and any other field where organic thin-film materials can be
applied.
Optics and Photonics
Series Editor: Le Nguyen Binh
Huawei Technologies, European Research Center, Munich, Germany
1. Thin-Film Organic Photonics
Molecular Layer Deposition and Applications
Tetsuzo Yoshimura
2. Guided Wave Photonics
Fundamentals and Applications with MATLAB®
Le Nguyen Binh
3. Nonlinear Optical Systems
Principles, Phenomena, and Advanced Signal Processing
Le Nguyen Binh and Dang Van Liet
4. Wireless and Guided Wave Electromagnetics
Fundamentals and Applications
Le Nguyen Binh
5. Guided Wave Optics and Photonic Devices
Shyamal Bhadra and Ajoy Ghatak
6. Digital Processing
Optical Transmission and Coherent Receiving Techniques
Le Nguyen Binh
7. P hotopolymers
Photoresist Materials, Processes, and Applications
Kenichiro Nakamura
8. O ptical Fiber Communication Systems with MATLAB® and Simulink® Models,
Second Edition
Le Nguyen Binh
9. Noises in Optical Communications and Photonic Systems
Le Nguyen Binh
10. Advanced Digital Optical Communications, Second Edition
Le Nguyen Binh
11. Optical Modulation: Advanced Techniques and Applications in Transmission
Systems and Networks
Le Nguyen Binh
12. Optical Multi-Bound Solitons
Le Nguyen Binh
Molecular Layer
Deposition for Tailored
Organic Thin-Film
Materials
Tetsuzo Yoshimura
Designed cover image: Naoko Yoshimura
First edition published 2023
by CRC Press
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and by CRC Press
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CRC Press is an imprint of Taylor & Francis Group, LLC
© 2023 Tetsuzo Yoshimura
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Library of Congress Cataloging‑in‑Publication Data
Names: Yoshimura, Tetsuzo, author.
Title: Molecular layer deposition for tailored organic thin-film materials / Tetsuzo Yoshimura.
Description: First edition. | Boca Raton : CRC Press, [2023] |
Series: Optics & photonics | Includes bibliographical references and index. |
Identifiers: LCCN 2022042617 (print) | LCCN 2022042618 (ebook) |
ISBN 9780367554743 (hardback) | ISBN 9780367555603 (paperback) | ISBN 9781003094012 (ebook)
Subjects: LCSH: Organic thin films. | Molecular electronics–Materials. |
Monomolecular films. | Quantum dots. | Atomic layer deposition.
Classification: LCC TK7872.T55 Y67 2023 (print) | LCC TK7872.T55 (ebook) |
DDC 621.3815/2–dc23/eng/20221206
LC record available at https://lccn.loc.gov/2022042617
LC ebook record available at https://lccn.loc.gov/2022042618
ISBN: 978-0-367-55474-3 (hbk)
ISBN: 978-0-367-55560-3 (pbk)
ISBN: 978-1-003-09401-2 (ebk)
DOI: 10.1201/9781003094012
Typeset in Times New Roman
by codeMantra
To the memory of my wife, Yoriko
Contents
Preface......................................................................................................................xv
Author ....................................................................................................................xvii
Chapter 1 Introduction ..........................................................................................1
Chapter 2 Examples of Inorganic Tailored Materials ...........................................7
2.1 Classification of Thin-Film Growth Methods ...........................7
2.2 Wavefunction Control in Quantum Corrals by Scanning
Tunneling Microscope ...............................................................8
2.3 Wavefunction Control in Photonic/Electronic Devices by
Molecular Beam Epitaxy .........................................................11
2.4 Amorphous Superlattices Fabricated by Plasma Chemical
Vapor Deposition .....................................................................14
2.4.1 Transfer Doping in a-SiN:H/a-Si:H Amorphous
x
Superlattices ...............................................................14
2.4.2 Influence of a-SiN:H Gate Insulator
x
Composition on Thin-Film Transistor Performance ..17
2.5 Wavefunction Control in Electrochromic Thin
Films by Sputtering .................................................................19
References ..........................................................................................24
Chapter 3 Molecular Layer Deposition (MLD) ..................................................27
3.1 Atomic Layer Deposition and Molecular Layer Deposition ....27
3.1.1 Atomic Layer Deposition ...........................................27
3.1.1.1 Concept of Atomic Layer Deposition .........27
3.1.1.2 Optoelectronic Materials and Devices
Expected to be Realized by ALD ...............29
3.1.2 Beginning of MLD .....................................................30
3.2 Concept of MLD ......................................................................31
3.2.1 Basic Concept of MLD ...............................................31
3.2.1.1 MLD Utilizing Chemical Reaction ............32
3.2.1.2 MLD Utilizing Electrostatic Force .............33
3.2.2 Variations of MLD .....................................................33
3.2.2.1 MLD Involving Steps for Side
Molecule Attachment and Cross-Linking ...33
3.2.2.2 MLD Utilizing Molecule Groups ...............36
3.2.2.3 Both-Side and Branching Wire Growth .....36
3.3 MLD Equipment ......................................................................37
vii
viii Contents
3.3.1 Vapor-Phase MLD ......................................................38
3.3.1.1 K-Cell-Type MLD .......................................38
3.3.1.2 Carrier-Gas-Type MLD ..............................38
3.3.2 Liquid-Phase MLD ....................................................40
3.3.3 MLD Utilizing Gas-Flow Circuits and
Fluidic Circuits ...........................................................41
3.4 Growth Mechanisms of MLD .................................................42
3.4.1 Growth Rates ..............................................................42
3.4.2 MLD Windows ...........................................................43
3.5 Proof of Concepts of Monomolecular-Step
Growth in MLD .......................................................................46
3.5.1 Polymer Wires Grown by MLD Utilizing
Chemical Reaction .....................................................46
3.5.1.1 Polyamic Acid Made from
PMDA/DNB ...............................................46
3.5.1.2 Polyimide Made from PMDA/DDE ...........48
3.5.1.3 Conjugated Polymers ..................................50
3.5.2 Molecular Stacked Structures Grown by MLD
Utilizing Electrostatic Force ......................................50
3.5.2.1 Stacked Structures of p-Type and
n-Type Dye Molecules on ZnO Surfaces ....51
3.5.2.2 Dye Adsorption Strength ............................54
3.5.2.3 LP-MLD with p-Type and n-Type Dye
Source Molecules ........................................57
3.5.2.4 LP-MLD Utilizing Molecule Groups .........60
3.5.2.5 Monomolecular-Step Growth of
Charge-Transfer Complexes ........................61
3.6 High-Rate MLD ......................................................................62
3.6.1 Influence of Molecular Gas Flow on Polymer
Film Growth ...............................................................62
3.6.2 Domain-Isolated MLD ...............................................62
References ..........................................................................................66
Chapter 4 Selective MLD ...................................................................................69
4.1 Classification of Selective Growth ..........................................69
4.2 Area-Selective Growth on Hydrophilic/Hydrophobic
Surfaces ...................................................................................69
4.2.1 Concept .......................................................................69
4.2.2 Area-Selective Growth of Poly-AM on SiO/
Hexamethyl-Disilazane (HMDS) Surfaces ................71
4.2.3 Area-Selective Growth of Poly-AM on SiO /
2
Triphenyldiamine (TPD) Surfaces .............................73
4.2.4 Area-Selective MLD of Polymer MQDs on TiO /
2
ZnO Surfaces ..............................................................73
Contents ix
4.3 Horizontally-Aligned Selective Growth on Anisotropic
Atomic-Scale Structures ..........................................................73
4.3.1 All-Dry Process for Polymer Wire Alignment ..........74
4.3.2 Poly-AM on Obliquely-Evaporated
SiO Underlayers ........................................................75
2
4.3.3 Poly-AM on Obliquely-Evaporated
SiO Underlayers ..........................................................79
4.3.4 Polyimide on Obliquely-Evaporated
SiO Underlayers ........................................................79
2
4.4 Electric-Field-Assisted Selective Growth ................................81
4.4.1 Concept .......................................................................81
4.4.2 Polyamic Acid ............................................................82
4.5 Vertically-Aligned Selective Growth from Seed Cores ..........83
4.5.1 Vertically-Aligned Selective MLD from Seed
Cores with Self-Assembled Monolayers (SAMs) .......83
4.5.1.1 Surface-Active Materials
for Seed Cores .............................................83
4.5.1.2 Vertically-Aligned Selective MLD of
Poly-AM from SAMs .................................84
4.5.1.3 Carrier-Gas-Type Organic CVD of
Poly-AM from SAMs .................................86
4.5.2 Monomolecular-Step Polymer Wire Growth
from SAMs .................................................................89
4.6 Improved Area-Selective Resolution .......................................92
References ..........................................................................................93
Chapter 5 Expected Impacts of MLD on Photonics/Electronics Field ...............95
5.1 Featured Capabilities of MLD.................................................95
5.2 Photonic/Electronic Devices Realized by MLD .....................96
5.2.1 Advanced Photonic/Electronic Devices .....................96
5.2.2 MLD Processes for Advanced Photonic/
Electronic Devices......................................................96
5.2.2.1 Devices with Conjugated Polymer
Wires Containing Donors/Acceptors ..........96
5.2.2.2 Area-/Orientation-Controlled Selective
MLD for Devices with Conjugated
Polymer Wires ..........................................100
5.3 Photonic/Electronic Molecular Nanosystems
Fabricated by MLD ...............................................................103
5.4 Molecular Nanoduplication (MND) ......................................105
References ........................................................................................108
Chapter 6 Polymer Multiple Quantum Dots (MQDs) Fabricated by MLD ......111
6.1 Quantum Dots .......................................................................111
