MALDI SIMS

Raster-scan technique

Raster scan

Vector scan

The e-beam is scanned in both x- and y-directions with beam blanking, writing the pattern pixel-by-pixel

Raster scan versus vector scan

Raster scan: Very simple and fast. Very repeatable But sparse patterns take as long as dense

patterns. Difficult to adjust dose during writing. For photo-mask making.

Raster scan

Vector scan

Vector scan: Fast writing of sparse patterns

(unwritten areas skipped). Easy dose variation from shape to

shape. For nanolithography and R&D.

Beam blanked here

Beam never pass here

Round (Gaussian beam) vs. shaped beam

Beam is focused to a round spot with size as small as possible for high resolution.

Slow since each pixel is small (order 10nm).

Used for R&D.

Beam is shaped to a rectangular shape for fast writing.

Fast since each pixel is large.

Mainly used for photo-mask making, with each square pixel size order 100nm.

Gaussian beam shaped beam

The use of Auger spectroscopy for the in situ elemental characterization of sub-micrometer presolar grains Frank J. STADERMANN, Christine FLOSS, Maitrayee BOSE and A. Scott LEA Meteoritics & Planetary Science 44, Nr 7, 10331049 (2009) Laboratory for Space Sciences, Physics Department, Washington University, CB 1105, Brookings Drive, St. Louis, Missouri 63130, USA; Pacific Northwest National Laboratory, Richland, Washington 99352, USA

Analise de contaminao superficial de um material

Determinao de composio em defeitos de Silicon wafer apos produo

A imagen no perminte observar nenhuma diferencia Devido ao tamanho das particulas(sub-m) EDS no permitiria obter informao de composio debido ao volume minimo de excitao

3) Construo da imagem com

respeito a intensidade de ons x

y

1) Varredura do feixe

pela superfcie

2) Espectro de massas em

cada ponto

m/z: 137- algodo

m/z: 402- sabo

50 m

In Cu Na

100 m

0 200 400 600 800 1000 1200 1400 1600 1800 2000

0

1k

2k

3k

4k

m/z

Co

un

ts

Sinal de ions

total

M+

M2+

Na+

Ag+

158+

J. S. Fletcher, N. P. Lockyer, S. Vaidyanathan, J. C. Vickerman, Tof-sims 3d biomolecular imaging of xenopus laevis oocytes using buckminsterfullerene (c-60) primary ions, Anal. Chem., 79 (2007) 2199. Manchester Interdisciplinary Biocentre, Centre for Instrumentation and Analytical Science, School of Chemical Engineering and Analytical Science, The University of Manchester, Manchester, M1 7ND, UK

S. Vaidyanathan, J. S. Fietcher, R. Goodacre, N. P. Lockyer, J. Micklefield, J. C. Vickerman, Subsurface biomolecular imaging of streptomyces coelicolor using secondary ion mass spectrometry, Anal. Chem., 80 (2008) 1942.

m/z: 30, 44, 60, 120, 130, 159, 170, 171, podem ser associados celulas de folculo que formam uma rede sobre a clula ovocitria.

Clulas anaplasticas de um carcinoma tanaplastic da tiroide carcinoma foram Rapidamente frozen, freeze dried e analisadas num instrumento TOF-SIMS de image 3D.

Images moleculares 3D de alta resoluo

HAKAN NYGREN, BIRGIT HAGENHOFF; PER MALMBERG, MIKAEL NILSSON, AND KATRIN RICHTER, Bioimaging TOF-SIMS: High Resolution 3D Imaging of Single Cells, MICROSCOPY RESEARCH AND TECHNIQUE 70:969974 (2007)

100m

Espectro TOF-SIMS de ons positivos utilizando o Bi3

+ liquid metal ion gun obtido aps 80 ciclos de varredura com ions C60 Cada ciclo tem 1600 varreduras. Imagem: 308 x 308 m2 e resoluo de 256 x 256 pixels. (a)Overlay image of the distribution of Na,

m/z 23, in red (Maximum counts (mc) 5 254) and the distribution of K, m/z 39, in green (mc 5 212)

(b) The distribution of the phosphocholine fragment m/z 86 (mc:59).

(c) The distribution of the phosphocholine headgroup, C5H15PNO4, m/z 184 (mc 5 38).

Na+ K+ 86+ (fragmento do grupo phosphocholine)

C5H15PNO4+, m/z = 184,

308 x 308 m

160m 60m 10m

Membrana intracelular

50m

Represents phosphocholine, the headgroup of the phospholipids phosphatidylcholine, and sphingomyelin;

Three-dimensional depth profiling of molecular structures, Wucher & J. Cheng & L. Zheng & N. Winograd, Anal Bioanal Chem (2009) 393:18351842.

Combinao de AFM e Cluster-SIMS

Imagem Modo microscpio Modo microprobe

C60q+, q = 1 .. 3

256 x 256 pixels

Tpicas dimenses de varredura: x = 200 m. y = x/cos . = 45o

Sistema prottipo: trehalose dopada com 1% de peptide (GGYR) sobre um substrato de Si. Espessura do filme: 300 nm.

AFM: KLATencor (NanoPix 2100).

1) Imagem de AFM

2) Cratera de 1.5 x 1015 Ga+/cm2 160 x 200 m2 e 30 nm de

profundidade.

3) PSU foi desenhada no filme

4) Imagem de AFM

5) 40-keV feixe de C60+ para obter uma imagem SIMS

Ga+

Peptide+ dentro do filme de trealose

Si+

Ga+ Peptide+ dentro do filme de trealose

Si+

Zheng L, Wucher A, Winograd N (2008) Anal Chem 80:73637371

Gated area depth profile of a multilayer stack of alternating LB films of about 50-nm width on Si measured using 40-keV C60

+ projectile ions for sputter erosion and data acquisition. The gating area was 25% of the eroded crater area (280200 m)

Desorption electrospray ionization (DESI)

MALDI

SIMS

50 50 m up to 1 1 mm

M.Stoecklia, T. B. Farmera, R. M. Caprioli; Journal of the American Society for Mass Spectrometry, 10. 1999, 6771

Mass spectrometry image (a) (50 50 pixels, 1.5 1.5 mm) at m/z 314 and optical image (b) of a letter printed with an ink printer.

Image of letters printed by an ink-jet printer (HP DeskJet 500).

hCG is a naturally occurring hormone that is produced by the placenta once a pregnancy is established. hCG is the hormone measured in the pregnancy test.

Chughtai, K.; Heeren, R. M. A., Mass Spectrometric Imaging for Biomedical Tissue Analysis. Chemical Reviews 2010, 110, (5), 3237-3277.

Mass spectrometric imaging (MSI).

Figure 22. Imaging of the ganglioside distribution in different brain regions: (A) an overview of the ganglioside distribution in different brain regions; (B) the distribution pattern of gangliosides in the hippocampus. Reprinted with permission from ref 268. Copyright 2008 Sugiura et al.

Hitchcock, A. P., Soft X-ray spectromicroscopy of polymers and biopolymer interfaces. Journal of Synchrotron Radiation 2001, 8, 66-71.

Fillers: styrene-acrylonitrile (SAN) and polyisocyanate poly-additionproduct (PIPA)-based particles

Polyurethanes

Microstructure of polyurea capsule walls

Protein-polymer interface studies

ELMITEC Elektronenmikroskopie GmbH

Photoelectron emission microscopy (PEEM) PEEM can be as simple as a straight microscope column accelerating the electrons in front of a sample and projecting a magnified image on the detector. However, it can also be extremely powerful by resolving the kinetic energy of the emitted electrons (XPEEM).

The intensity of total photoelectrons emitted from the surface is proportional to the absorption of Xray. By scanning the energy of X-ray around the absorption edge, the NEXAFS spectra in all microscopic regions in a PEEM image. can observe SiSiO2 micro-patterns were made in the sample surface by low energy implantation as follows. 3 keV O2 + ions were implanted in Si (0 0 1) wafer using a rectangular mask of 12.5 m periodicity (5 m blank and 7.5 m space). After the ion implantation, the mask was taken off in the atmosphere. Monte Carlo Simulation: the averaged depth of the implanted oxygen was about 30 nm.

The lateral surface diffusion at SiSiO2 interface has been observed at nanometer scale using photoelectron emission microscopy (PEEM) combined with synchrotron soft X-ray excitation.

Hirao, N.; Baba, Y.; Sekiguchi, T.; Shimoyama, I.; Honda, M., Microscopic observation of lateral diffusion at SiSiO2 interface by photoelectron emission microscopy using synchrotron radiation. Applied Surface Science 2011, 258, (3), 987-990.

Hirao, N.; Baba, Y.; Sekiguchi, T.; Shimoyama, I.; Honda, M., Microscopic observation of lateral diffusion at SiSiO2 interface by photoelectron emission microscopy using synchrotron radiation. Applied Surface Science 2011, 258, (3), 987-990.

1841 eV

1847 eV

1844.6 eV

Concluses

Partculas carregadas: Varredura do feixe por campos eltricos (x, y)

Laser: movimentao da amostra

Modos microfoco ou microscpio

Resoluo lateral: eltron > ons > X-rays > laser Sputtring: Permite imagen 3D

NEXAFS