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Cursul 6

Metode de autoasamblare Metode de crestere prin matrite (template)

Titularul de disciplin:Prof. Dr. Ing. Dan Dasclu Cerc.st. gr. I, dr. Ing. Mircea Dragoman Dr. Emil Mihai Pavelescu (IMT). mircea.dragoman@imt.ro

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Semiconductor doping Semiconductor doping is a key technological process in microelectronics and accompanies the deposition processes. It is well known that p- or n-doping of a semiconductor changes significantly the electrical, chemical and mechanical characteristics of semiconductors. These changes are often referred to as the functionalization or engineering of the material. The electrical changes are used to produce almost any active electronic component, such as transistors and diodes, while the mechanical changes create MEMS devices with prescribed mechanical characteristics . Impurities of p- or n-type are controllable introduced in intrinsic silicon via diffusion into furnaces at high temperatures from liquid or solid sources or via ion implantation techniques, which are more accurate with respect to the amount of impurities/area and the prescribed impurity profile. The variety of functionalization techniques at nanoscale is much richer compared to that of microscale transistors, diodes and integrated circuits. The doping is still used, for example, for nanotube transistors, but the functionalization of nanowires or dots can be done via oxygenation, hydrogenation, adsorbing of molecules, biomolecules etc Doping by diffusion Typical doping concentration 1015-1019 atoms/cm3

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Doping at the nanoscale 1 single impurity atom

500 C atomslength 15 nm
One C atom missiing- a defect

Resistance is increased 3 orders of magnitudes

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SUBMICRON TECHNOLOGY NANOTECHNOLOGY ATOM TECHNOLOGY

EB FIB EUV Optical 1000 100 Nanoimprint 10 1

AFM, STM Atom lithography


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0.1

Feature size (nm)

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Self-Assembly Techniques
The self-assembly process refers to the spontaneous organization of various components (molecules or various nanosize objects such as nanoparticles) into a single, ordered aggregate. The organization process is made into a desired structure via physical, chemical, or biochemical interactive processes involving, for example, electrostatic and surface forces, hydrophobic and hydrophilic chemical interactions. All these processes, irrespective of their origin, are very selective and reject defects so that the resulting desired structure is characterized by a high degree of perfection

The Langmuir-Blodgett (LB) technique dedicated to thin film realization is a well spread selfassembly technique in which the organized aggregate is built by growing one monolayer at a time. A monolayer of a desired material, which is initially adsorbed at a gas-liquid interface, is transported to a substrate on which the self-assembly structure will be grown. For example, a monolayer of some molecular species, such as a fatty acid, is spread over the surface of the water. In the water there is a glass microscope slide, which plays the role of the self-assembly substrate. If we pull out the glass slide the monolayer will be attached to it. If we then pass the glass slide several times through the water surface we will deposit on it a monolayer at each passing .The LB technique is implemented with specialized instruments comprising a Langmuir trough, a dipping device for the substrate that will be raised or lowered, and a movable barrier controlled by a pressure sensor, which slides on the gas-liquid interface to maintain a certain surface pressure

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Monolayer Glass plate Fat acid

Water

LB technique
Although 2D gold, nanoparticle arrays, semiconducting quantum dots and polymeric films were realized using the LB technique, the method is quite difficult and requir esexpensive instrumentation

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The electrostatic self-assembly is realized through the electrostatic
interaction between molecules or nanoparticles. This self-assembly technique originates from the fabrication of multilayer films where each layer is composed of positive- and negative-charged colloid particles such as Si and Al. The method is widespread in the implementation of nanostructured films containing metals, semiconductors, magnetic materials, polymers, or organic molecules. The resulting film is uniform and stable due to strong ionic bonds between negative- and positive-charged particles, and the defects are minimized due to the repulsive force between the particles involved in the process. The utilization of polymers in combination with layers of charged nanoparticles is the best way to minimize the defects. The electrostatic self-assembly process starts with the immersion of a clean substrate into a cationic solution, followed by a dip of the substrate coated with cations into an anionic solution where the adsorption of anionic molecules takes place at a molecular level. For example, positively charged gold nanoparticles are self-assembled on a negative glass substrate by immersion into 4ATP(aminotiophenol)-capped gold solution with pH = 4. A layer of negatively charged Ag nanoparticles can be further deposited by immersion of the glass coated with Au particles into a 4-CTP(carboxythiophenol)-capped silver solution with pH = 8.5 Thus, it is possible to obtain a heterostructure consisting of successive layers of Au and Ag nanoparticles.

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RINSE DRY RINSE
water

DRY

Cationic solution

Water

Anionic solution

Water

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The chemical self-assembly methods are the most commonly used techniques. Among them, SAM (self-assembled monolayers) and MPC (monolayer-protected clusters) are the most prominent. SAM deals with the spontaneous formation of monolayers via immersion of a suitable substrate into a solution, while MPC refers to nanoclusters whose surface is derivatized by ligand molecules with the help of chemisorption Biomolecular self-assembly uses DNA or proteins as basic constituents to realize: 1) biomolecular-metal complexes such as DNA-Au complexes, 2) self-assembly of semiconducting nanoparticles such as CdSe quantum dot ensembles, or 3) functionalized metallic nanoparticles.
Au substrate Alkanethiol molecules Au nanoparticle

SAM

MPC

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DNA origami

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Nanoparticles The physical properties, and especially the electronic structure of

metal nano-

particles, are very different from those of bulk metals and are strongly dependent
on their size. For example, the conduction band of bulk metals is replaced by discrete energy states in a metal nanoparticle. Thus, the metal particle behaves like a quantum dot, in which electrons are confined in all directions, in contrast with the free electrons of bulk metals. Metal particles covered with organic molecules such as thiols are able to self-organize in 1D, 2D and 3D arrays. The discreteness of electronic states in a metal nanoparticle is characterized by the Kubo gap (i.e., the average spacing between successive quantum levels)

4EF / 3n
where EF is the Fermi energy, and n is the number of electrons in the nanoparticle. The nanoparticle is metallic if :

kBT

For example, a silver particle with a diameter of 3 nm, for which = 10 meV, is metallic at room temperature since kBT =25 meV for T = 300 K.

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CdS (semiconductor nanoparticles)

CdS (semiconductor nanoparticles)

Gold substrate

Gold substrate

There are not only metal nanoparticles, but also semiconductor nanoparticles such as silicon nanoparticles, III-V nanoclusters, elemental II-VI semiconductor quantum dots in solution or gaseous phases.

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Nanowires
A nanowire is a metallic, semiconducting, superconducting or magnetic physical system, which is confined in two dimensions. The nanowire has a transverse area of a few nm and can attain 100300 nm in length, although longer nanowires, up to 1 m, have also been fabricated. Nanowires can be realized via many methods.
Source material Anodized alumina

Template synthesis

Aluminium

Cracks

SiO2

Metal

Nanowire array

Top view

Self assembly
Si Si

Si

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Nanowires with ultra-small diameters are grown using CVD or MOCVD. The nanowire precursor material is heated to produce vapors that penetrate the nanopores of the template, which is then cooled to get the solidified nanowires. Nearly single-crystal nanowires are obtained with the CVD method, while in the rest of the above-mentioned methods mainly polycrystalline nano-wires are fabricated. Single-crystal nanowires of Bi, GaN, GaAs, and InAs, with diameters less than 10 nm, can be grown with the CVD techniques. Carbon nanotubes (CNTs), are also grown in alumina templates via CVD techniques. CNTs with very small diameters, of a few nm, can be grown by replacing the alumina template with a zeolite template.The vapor-liquid-solid (VLS) nanowire growth method is based on the fact that the vapors (V) of the source material can be absorbed into a liquid (L) droplet of a catalyst. The nanowire is obtained due to the solidification (S) of the source material as a result of the saturation of the liquid alloy followed by a nucleation process, which creates a preferential site for further deposition at the liquid boundary.

Vapors (V)

Liquid catalyst (L) Growth direction Nanowire (S)

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Millions of CNTs can be aligned and integrated using a large-scale assembly technique inspired from biomolecular self-assembly processes . In this method, chemically functionalized patterns on a surface are first realized, on which millions of CNTs spread in a solution are then aligned. Two distinct regions coated via direct deposition with polar groups and nonpolar groups, respectively, create the functionalization of the surface. By placing the functionalized surface into a liquid suspension containing millions of CNTs the nanotubes are attracted by the polar regions and millions of CNTs are aligned in less than 10 s, The electrostatic attraction force rotates the CNTs towards the polar region and confines them only in this region. The efficiency of alignment is very high, of about 90%.
Polar region Nonpolar region Rotation towards polar region

Gold surface

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Dielectrophoresis (or DEP) is a phenomenon in which a force is exerted on a dielectric particle when it is subjected to a non-uniform electric All particles exhibit dielectrophoretic activity in the presence of electric fields. However, the strength of the force depends strongly on the medium and particles' electrical properties, on the particles' shape and size, as well as on the frequency of the electric field. Consequently, fields of a particular frequency can manipulate particles with great selectivity. This has allowed, for example, the separation of cells or the orientation and manipulation of nanoparticles and nanowires.

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CNT interconnect

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Al template

Si nanowire

GaN

CNT

ZnO

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CNT arrays ZnO nanohelix