Synthesis and Characterization of

Cadmium Sulfide (CdS) Nanowires (NWs)

Edward Bujak and Dr. Ritesh Agarwal

RET Program – University of Pennsylvania

Department of Materials Science and Engineering

and

Laboratory for Research on the Structure of Matter

University of Pennsylvania, PA, 19104-6272

July 27, 2006

ABSTRACT

Nanostructures have been investigated extensively using various compounds that

exhibit novel, peculiar, and fascinating properties in the nano scale not exhibited in the

bulk materials or superior to their bulk counterparts, such as: optical, electrical,

biological, mechanical, and chemical aspects, with various morphologies such as rods,

belts, ribbons, wire, helices, dots, and tubes. Dramatic progress has been made in the

investigation and application of these structures stimulating further research and

investment.

Semiconductor nanowires have been a focus of attention for nano-electronics and

nano-optics (or nano-optoelectronics). Specifically, cadmium sulfide (CdS) is a

semiconductor with a large and direct bandgap of Eg = 2.42 eV at room temperature

which, upon excitation, emits light of wavelength 517 nm ( λ excitation~517nm). Due to

these unique properties, CdS is one of the most promising materials in optics devices.

This study’s main focus is on the synthesis and characterization of cadmium

sulfide nanowires (CdS NWs). Using conventional VLS growth, the NW synthesis was

performed with a custom made horizontal furnace chemical vapor deposition (CVD)

system. Colloidal Au nanoparticles were used as a catalyst with later studies using

sputtered Pt as a catalyst. The optimal condition for nanowire growth was established

varying process temperature, vacuum pressure, gas flow rate, and the diameter of the

catalyst. Characterization on morphology, crystal structure and chemical composition

were done using Optical microscopy, Scanning Electron microscopy (SEM),

Transmission Electron microscopy (TEM), High Resolution Transmission Electron

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microscopy (HRTEM), and X-ray Energy Dispersive Spectroscopy (EDS or EDX) in

STEM mode.

The morphology and the diameter of the nanowires were defined in controlled

fashion using different catalyst deposition methods and different sizes of catalyst (20-

100nm). We conclude that the dominant process parameter for optimal growth were the

temperature of the substrate and the concentration of the precursor. Further

characterization on optical properties is on the way.

INTRODUCTION

The field of electronics continues to grow and expand, but limits to progress are

falling to new and exciting possibilities. Microelectronics revitalized the fields of

telecommunication and technology through the bulk properties of materials in the

production of microchips and integrated circuits that contained millions of linked

semiconducting devices on the scale of µm (10-6 m). In the near future, nanoelectronic

devices may replace microelectronics in communication and computer industries with

nanostructures having one dimension between 1 and 100 nm.5 The emerging field of

nanoelectronics, electronics on the nanoscale, has the potential to take electronics, as well

as other fields, further than ever imagined. 1,11 This is possible because reducing the size

of a semiconductor to nanoscale proportions alters its bulk electronic, magnetic, and

optical properties.10 These enhanced properties enable multiple new applications

including the integration of nanomaterials into nanodevices such as biological imaging

and biolabeling14 , semiconducting nanowire high efficiency photovoltaic (PV) solar

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cells, waveguides, lasers, light emitting diodes (LED), optoelectronic devices, and a wide

array of photosensors, such as: photoresistors, photoconductive devices, photodetectors,

photodiodes, phototransistors, photodarlingtons, and slotted and reflective optical

switches.2 Various nanostructure morphologies have been synthesized such as: rods,

belts, ribbons, spheres, helices, dots, tubes (single walled SWNT and double walled

(DWNT), branches (whiskers or dendritic), and core-shell (coaxial), to name a few, to

capitalize on their unique form and contour. In particular, semiconductor nanowires, in

which one dimension is approximately 100 times the other dimension, represent a broad

class of nanoscale building blocks that have been successfully used to assemble a wide

range of electronic and photonic devices.

We study CdS because it has novel optical properties; namely its high

photoluminescence (PL) quantum efficiency.15 The energy band gap of CdS is direct

and large (wide). An electron will emit energy (E= hν ) in falling from an excited state to

Figure 1. Generic energy band gap.

a ground state., but can fall directly or indirectly. With indirect band gap materials, the

electron in the conduction band moves to the point of energy minima at the expense of

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kinetic momentum. In indirect band gap materials, the electrons in the conductive band

need some source of momentum to reach the minimum and fall into the holes in the

valence band. With indirect energy band gap materials, the electron falls through one or

more intermediate energy bands so the emission of energy is gradual and an inefficient

source of light emission.

Figure 2. Direct band gap (GaAs) and indirect band gap (Si).

In a material with a direct energy band gap, such as CdS, the electron falls in one

step resulting in a faster, more concentrated emission of energy since the conductive band

is directly combined with the valence band, conserving kinetic energy. The energy that is

produced is emitted as a photon (light particle or quanta) and is therefore used in

applications such as solar cells and light-emitting diodes (LED). 1

The energy band gap of CdS is also large (wide) resulting in a relatively large

released energy than materials with a smaller energy band gap. The energy band gap for

CdS is 2.42eV (Eg = 2.42 eV ); corresponding to an excitation wavelength of

approximately 517 nm ( λ Excitation~517nm=5170Å). Alternatively, a current can be

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measured when the CdS nanowires are exposed to light of wavelength smaller than 517

nm.

Technically the band gap is the energy difference between the valence band and

the conduction band or it is the energy required to break the chemical bonds thereby

producing free electrons and holes. From a practical point of view, the band gap energy

(Eg ) represents a lower limit on the photon energy necessary to cause a change in

resistance. Photons incident on these materials must have an energy hν > Eg (or a lower

wavelength than its emitted wavelength) in order to cause a change in resistance. Eg is

the band gap in electron volts (eV), h is Planck’s constant (4.13566743 x 10-15 eV·s or

6.626 x 10-34 J·s) and ν is the frequency of the light (s-1). We also know c = λν , where

c is the speed of light (299,792,458 m/s) and λ is the wavelength (m).

Band Gap Wavelength Frequency

Name of Semiconductor (eV) at 300K (nm) (T Hz)
Cadmium sulphide (CdS) 2.4 517 580
Cadmium Phosphide (CdP) 2.2 564 532
Cadmium Selenide (CdSe) 1.7 729 411
Gallium Arsenide (GaAs) 1.4 886 338
Silicon (Si) 1.1 1127 266
Germanium (Ge) 0.7 1771 169
Indium Arsenide (InAs) 0.43 2883 104
Lead Sulphide (PbS) 0.37 3351 89
Lead Telluride (PbTe) 0.29 4275 70
Lead Selenide (PbSe) 0.26 4769 63
Indium Antimonide (InSb) 0.23 5390 56
Table 1. Photoresistive semiconductor materials.
Derived from band gap data presented at
http://www.thiel.edu/digitalelectronics/chapters/apph_html/apph.htm 13

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 The peak sensitivity for photoresistors occurs at a frequency somewhat larger than

that determined by the band gap energy or equivalently at a wavelength somewhat

shorter than the wavelength determined by the band gap and falls off on either side. The

wavelength sensitivity for CdS, CdSe and CdTe normalized to a peak of 1 in each case is

shown in Figure 5. Note that the peak wavelength of CdS is at 5180 Å (518 nm) or a low

wavelength green

Figure 3. CdS Photoresistive detectors.

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 Figure 4. Electromagnetic/Visible Spectrum.
Source: http://en.wikipedia.org/wiki/Electromagnetic_spectrum

Figure 5. Normalized sensitivities of CdS, CdSe, and CdTe as a function of wavelength.

Source: http://www.thiel.edu/digitalelectronics/chapters/apph html/apph.htm 13

8
 color wavelength interval frequency interval

red ~ 625–740 nm ~ 480–405 THz

orange ~ 590–625 nm ~ 510–480 THz

yellow ~ 565–590 nm ~ 530–510 THz

green ~ 500–565 nm ~ 600–530 THz

cyan ~ 485–500 nm ~ 620–600 THz

blue ~ 440–485 nm ~ 680–620 THz

violet ~ 380–440 nm ~ 790–680 THz

Table 2. The colors of the visible light spectrum.
Source: source: http://en.wikipedia.org/wiki/Color

Color nm 1014 Hz 104 cm−1 eV kJ mol−1

Infrared >1000 <3.00 <1.00 <1.24 <120
Red 700 4.28 1.43 1.77 171
Orange 620 4.84 1.61 2 193
Yellow 580 5.17 1.72 2.14 206
Green 530 5.66 1.89 2.34 226
Blue 470 6.38 2.13 2.64 254
Violet 420 7.14 2.38 2.95 285
Near ultraviolet 300 10 3.33 4.15 400
Far ultraviolet <200 >15.0 >5.00 >6.20 >598

Table 3. Color, wavelength, frequency and energy of light

source: http://en.wikipedia.org/wiki/Color

For the synthesis of CdS nanowires, it is necessary to understand the

thermodynamics of its formation. Figure 6 is the pseudo-binary phase diagram for gold

(Au) and cadmium sulfide (CdS) that illustrate the thermodynamics of vapor-liquid-solid

(VLS) growth. Note that this phase diagram shows that Au and CdS are partially soluble

in each other. This consists of the phases that pass the Au/CdS interface during the

temperature and time (concentrations) of the reaction. At a process temperature near

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800°C, the CdS in the vapor phase causes the solid nanoparticles (1) to form a liquid

alloy L (Au+CdS), and with an increasing concentration of CdS will cause a

supersaturation in the alloy (2), that will lead nucleation of the solid CdS growing the

nanowires. Figure 7 shows the diffusion process directly from the colloidal nanoparticles

of Au and the interaction with the CdS in the vapor phase.

Figure 6. Pseudo-binary
Au-CdS phase diagram.

1Æ2 3

1Æ2 3

Figure 7. Nanowire growth.

Figure 8. CdS vapor diffusion through Au
catalyst for nanowire growth.

In this study our major interest was the synthesis and characterization of

nanowires, especially cadmium sulfide. It was necessary to determine the optimal

parameters for the synthesis such as: process temperature, argon (Ar) flow rate, vacuum

10
pressure, the catalyst and its diameter, and the concentration of the CdS precursor

(Cadmium Dimethylthiocarbonate).

The vapor-liquid-solid
Manometers:
Digital Gauge
(VLS) method was used for the Analog Gauge Venting Valve

Main Valve
fabrication of CdS nanowires. Quartz Tube
MFC Tube Furnace LN2 Trap

Ar Gas
This method has been reliably
RP Exhaust
used for over a decade for
Pressure displays and control

producing one dimensional MFC display and control

nanowires. VLS consists of two Figure 9. Horizontal LPCVD (low pressure chemical
vapor deposition) schematic.
main processes: evaporation and

condensation. Evaporation of the powder precursor is accomplished through high heat

(~800°C). Within a sealed quartz tube held at low pressure (~300 torr), the slowly

vaporizing precursor is carried through a by an inert Ar delivery gas to the Si <100>

substrate (~100 SCCM). The substrate is coated with a Au catalyst to stimulate the

nucleation and growth of the Tube Furnace

Quartz Tube
CdS crystalline structure to Ar Flow

form one-dimensional CdS Precursor: Si (100) Substrate

Cadmium Dimethylthiocarbonate Substrate Temp = 680°C
Process Temp = 780°C
nanowires. By using colloidal
Figure 10. Loaded quartz tube schematic .
Au particles as the catalyst in this

technique, the morphology of the CdS nanowires growth is precisely controlled; the

synthesized nanowire diameters are the diameter of the colloidal Au particle. . The

process time was about 15 minutes. For the structural characterization of the nanowires,

we used optical microscopy, scanning electron microscopy (SEM), transmission electron

11
microscopy (TEM), and high resolution transmission electron microscopy (HRTEM).

For the compositional characterization of the nanowires, we used X-ray Energy

dispersive spectroscopy (EDS).

MATERIALS AND METHODS

Substrate Preparation

• Cut the Si <100> substrate into ~0.5 cm wide strip (Figure 11).

• Rinse the Si substrate with acetone or ethyl alcohol (to remove organic materials).

• Rinse with de-ionized water.

• Blow dry with air.

• Apply poly-L-lysine solution to clean substrate and leave 5-10 minutes. The poly-L-

lysine created a positive charge to aid in the adhesion of the nanoparticle gold (Au)

catalyst.

• Lightly blow dry with air.

• Apply catalyst to substrate: colloidal gold nanoparticle solution to substrate (Au 20-

40 nm) with clean Pasteur pipette (Figure 12).

• Lightly blow dry with air.

Figure 11. Cutting Si <100> substrate. Figure 12. Application of Au catalyst.

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Quartz Tube Preparation

• Under a chemical fume hood:

• Place prepared substrate into end of quartz tube.

• Load precursor into combustion “boat”/ring (Figure 13) and place into

opposite end of quartz tube with a steel bolt.

• Place quartz tube into tube furnace, place glass wool at end of tube (Figures 15,16).

Figure 14. Placing CdS precursor

“boat”/ring into quartz tube.

Figure 13. Placing CdS

precursor into “boat”/ring.

Figure 15. Placing prepared quartz tube into

furnace.
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 Glass wool

Precursor
powder in
“boat”

Ar f
low

Ar f
low

Tube Furnace
Bolt to
Substrate push
precursor
in slowly

Figure 16. Prepared loaded furnace.

Fabrication/Synthesis of Nanowires

• Install liquid nitrogen trap into system and fill with liquid nitrogen.

• With vacuum pump:

• Check vacuum of system (assure sustained 20 m torr vacuum test).

• After integrity test (above), set operating low pressure vacuum (~300 torr).

• Start Ar carrier gas flow (~100 SCCM).

• Start tube furnace. The temperature of the process must be at least 750°C (typically

~800°C). The temperature at the edges of the furnace, input where the precursor

“boat”/ring is and output where the substrate is placed is typically 70-100°C less.

• Once operating temperature is reached, slowly push the precursor “boat”/ring into the

furnace with a bolt moved by a magnet.

• After a desired growth time (~15 minutes), stop tube furnace, let cool down.

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• After near room temperature, stop Ar flow, vent vacuum, and disassemble quartz tube

from furnace.

• Under a chemical fume hood, remove substrate with grown nanowires and safely

dispose of all hazardous materials.

• If this is last fabrication of the day, remove the liquid nitrogen trap and place in

chemical fume hood.

Pressure and vacuum

displays and controls
Valves

Argon Gas and LN2 Trap Tube Furnace

Regulator (25-1100°C)
Manometers:
digital gauge (30-765
torr) and analog
gauge (0-100 m torr)

Rotary (vacuum)
Pump
MFC
(100 SCCM)

Figure 17. LPCVD apparatus.

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RESULTS AND DISCUSSION

Characterization – Structure - Imaging – Optical Microscope

The nanostructures were first

examined directly on the Si substrate with

optical microscopes (Figure 18). If the

morphology and dimensions were

desirable, we then processed the nanowires

for electron microscopy.

Figure 18. Initial inspection of synthesized

NWs with optical microscope.

Characterization – Structure - Imaging - Electron Microscopy

(SEM/TEM/HRTEM)

We removed the “good” CdS

nanoparticles from the Si substrate by

scraping the particles off into a small vial,

mixed with acetone, and sonicated it to

disperse the particles uniformly in

suspension. With a Pasteur pipette we

Figure 19. Petri dish with multiple TEM
placed drops of the processed nanoparticles grids.

onto a TEM grid. We optionally make a few TEM grids and let air dry. We mounted the

TEM grid into the TEM scanning assembly (Figure 20) and placed it into the TEM

(Figure 21).

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 Figure 20. TEM grid is mounted Figure 21. TEM assembly is
on tip of TEM assembly. inserted into TEM.

The structures of the synthesized products were characterized using scanning

electron microscopy (SEM). Figure 22(a) and 22(b) shows the SEM images of the

nanowires grown on the Si at a temperature of 650°C. The CdS nanowires have diameters

between 50-150nm and lengths up to 30µm as shown in the SEM images.

Figure 22. SEM images of CdS NWs grown in large scale.

NW diameter: 50-150nm, length: up to 30 µm.

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 The morphology of CdS nanowires was observed in a transmission electron

microscope (TEM). Figure 23(a) is a typical TEM image, which demonstrates the general

view of the CdS nanowires. Figure 23(b) is a High-Resolution TEM (HRTEM) image

showing the uniformity of the grown nanowires. Figure 23(c) shows an equivalent image

of the CdS nanowires demonstrating the single crystalline nature.

002 002

5 nm

Figure 23. (a) TEM image of CdS NWs (b) HRTEM image (c) Fourier Transform of
HRTEM image.

Characterization – Composition – Energy Dispersive X-Ray Spectroscopy

(EDX or EDS)

Energy Dispersive X-Ray Spectroscopy (EDX or EDS) analysis was utilized to

characterize the chemical composition of the nanowires. Figure 24 shows a diffraction

pattern of single-crystalline CdS nanowires. The graphs (counts on the y-axis for a certain

emitted Energy eV on the x-axis) demonstrate that the bodies of the nanowires are

basically composed of Cadmium with a peak between 0.0-5.0 eV and a peak of Sulfide in

the same range. It can be observed, in the second graph, that the tip of the nanowires is

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composed almost completely of gold (Au) with a peak between 0.0-5.0 eV and a wide

peak between 5.0-10.0 eV.

The high peak in the second graph is an artifact from the Molybdenum (Mo) TEM

grid. The peak, between 10.0-15.0 eV, is unknown but didn’t cause any alteration in the

analysis of the graphs.

CdS
nanowire

??
Au Catalyst

20 nm

Molybdenum count spike due to Mo TEM grid

Figure 24. EDX/EDS images

CONCLUSION

We successfully synthesized CdS nanowires under controlled conditions with an

established protocol utilizing a simple Vapor-Liquid-Solid mechanism at low pressure

(LPCVD) We observed different nanowire growth by varying process parameters such

as: temperature (700°C-780°C), time (5-10 minutes), vacuum pressure (~300 torr),

19
carrier-delivery flow (100-300 SCCM), and catalyst (Au ~20-40nm nanocolloidal

particles and sputtered Pt). We observed that the major factors affecting desirable

nanowire morphology and density were concentration of the vapor delivered to the

substrate/catalyst and the process temperature.

Structurally we imaged the fabricated CdS nanowires with scanning electron

microscope (SEM), transmission electron microscope (TEM, and high-resolution

transmission electron microscope (HRTEM) which occasionally showed good nanowire

morphologies of length to width: long and thin.

Compositionally we examined the purity, density, and chemical makeup of the

CdS nanowire, utilizing Energy Dispersive X-Ray Spectroscopy (EDS or EDX) which

showed a uniform and high concentration of Cd and S across the nanowires with little or

no Au or Pt catalyst. Similarly the catalyst at the tip of the nanowires was effectively pure

Au or Pt and do not show any Cd or S peaks.

Optically, CdS is a very interesting photoluminescence (PL) material.

Unfortunately in this time frame we did not have time to investigate these. I understand

what is needed to realize this, but it was a limitation of available equipment.

ACKNOWLEDGEMENTS

I would like to thank the National Science Foundation’s (NSF) funding of the

Research Experience for Teachers (RET) and Dr. Andrew McGhie for this wonderful

opportunity to provide me and other teachers an experience in advanced exploratory

scientific discovery and research. Specifically I would like to thank my advisor Dr.

Ritesh Agarwal and his group of graduate and post doctoral students: Dr. Se-Ho Lee

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(Lee), Yeonwoong Jung (Eric), Dong-Kyun Ko (Ko), Yu-Han Cheng (Valorie), Xuelian

Zhu (Julian), and undergraduate student Andrew Jennings. Furthermore I would like to

thank fellow visiting individuals in this group: Maria Lòpez (REU-Research Experience

for Undergraduates, University of Puerto Rico), Dr. Spirit Tlali (Collaborative with

Southern Africa – Lesotho), and Dr. Murrell Dobbins (RET-Nanotechnology-Drexel

University) for their assistance and support.

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